- New Bromine-Containing Bis(arylimino)acenaphthenes and Related Metal Complexes
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Abstract: The condensation reactions of 5-bromoacenaphthenequinone with 2,6-diisopropylaniline and 4?bromo-2,6-di-iso-propylaniline afford new mono- and tribromosubstituted bis(arylimino)acenaphthenes: 1,2-bis[(2,6-diisopropylphenyl)imino]-5-bromacenaphthene (Dpp-Br-Bian) (L1) and 1,2-bis[(4-bromo-2,6-diisopropylphenyl)imino]-5-bromacenaphthene (p-Br-Dpp-Br-Bian) (L2), respectively. Compounds L1 and L2 act as neutral ligands in the [(Dpp-Br-Bian)ZnCl2] (I), [(p-Br-Dpp-Br-Bian)AlCl3] (III), and [(p-Br-Dpp-Br-Bian)GaCl3] (IV) complexes synthesized by the reactions of free diimines with the corresponding metal chlorides. The reaction of the known dibromosubstituted derivative 1,2-bis[(4-bromo-2,6-di-iso-propylphenyl)iminoacenaphthene (p-Br-Dpp-Bian) (L3) with copper(I) chloride also affords complex [(p-Br-Dpp-Bian)CuCl] (II) with the neutral diimine ligand. New compounds L1, L2, and I–IV are characterized by NMR, IR spectroscopy, and elemental analysis. The molecular structure of complex I is determined by X-ray structure analysis.
- Baranov, E. V.,Dodonov, V. A.,Fedushkin, I. L.,Koptseva, T. S.,Makarov, V. M.,Skatova, A. A.,Sokolov, V. G.
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Read Online
- Synthesis method of diafenthiuron impurity D
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The invention provides a preparation method of the diafenthiuron impurity D. According to the preparation method of the diafenthiuron impurity D, 2, 6-isopropylaniline, phenol, CS2 and the like are used as raw materials, a material basis is provided for regularly researching the impurities, and the method can also be used for qualitative and quantitative analysis of the impurities in diafenthiuron production. And the impurities are controlled within a safe and reasonable limit range, so that the quality standard of the diafenthiuron can be improved, and important guiding significance is provided for safe medication of the masses.
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Paragraph 0023; 0031-0035
(2021/08/06)
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- Synthesis method of diafenthiuron impurities A and B
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The invention provides a preparation method of the diafenthiuron impurities A and B. 2, 6-isopropylaniline, phenol, triphosgene, tert-butylamine and tert-butyl formamidine hydrochloride are used as raw materials, a material basis is provided for normatively researching the impurities, and the method can also be used for qualitative and quantitative analysis of the impurities in diafenthiuron production. And the impurities are controlled within a safe and reasonable limit range, so that the quality standard of the diafenthiuron can be improved, and important guiding significance is provided for safe medication of the masses.
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Paragraph 0037-0039
(2021/08/06)
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- London Dispersion Interactions Rather than Steric Hindrance Determine the Enantioselectivity of the Corey–Bakshi–Shibata Reduction
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The well-known Corey–Bakshi–Shibata (CBS) reduction is a powerful method for the asymmetric synthesis of alcohols from prochiral ketones, often featuring high yields and excellent selectivities. While steric repulsion has been regarded as the key director of the observed high enantioselectivity for many years, we show that London dispersion (LD) interactions are at least as important for enantiodiscrimination. We exemplify this through a combination of detailed computational and experimental studies for a series of modified CBS catalysts equipped with dispersion energy donors (DEDs) in the catalysts and the substrates. Our results demonstrate that attractive LD interactions between the catalyst and the substrate, rather than steric repulsion, determine the selectivity. As a key outcome of our study, we were able to improve the catalyst design for some challenging CBS reductions.
- Eschmann, Christian,Song, Lijuan,Schreiner, Peter R.
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supporting information
p. 4823 - 4832
(2021/02/01)
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- Development of effective bidentate diphosphine ligands of ruthenium catalysts toward practical hydrogenation of carboxylic acids
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Hydrogenation of carboxylic acids (CAs) to alcohols represents one of the most ideal reduction methods for utilizing abundant CAs as alternative carbon and energy sources. However, systematic studies on the effects of metal-to-ligand relationships on the catalytic activity of metal complex catalysts are scarce. We previously demonstrated a rational methodology for CA hydrogenation, in which CA-derived cationic metal carboxylate [(PP)M(OCOR)]+ (M = Ru and Re; P = one P coordination) served as the catalyst prototype for CA self-induced CA hydrogenation. Herein, we report systematic trial- and-error studies on how we could achieve higher catalytic activity by modifying the structure of bidentate diphosphine (PP) ligands of molecular Ru catalysts. Carbon chains connecting two P atoms as well as Ar groups substituted on the P atoms of PP ligands were intensively varied, and the induction of active Ru catalysts from precatalyst Ru(acac)3 was surveyed extensively. As a result, the activity and durability of the (PP)Ru catalyst substantially increased compared to those of other molecular Ru catalyst systems, including our original Ru catalysts. The results validate our approach for improving the catalyst performance, which would benefit further advancement of CA self-induced CA hydrogenation.
- Saito, Susumu,Wen, Ke,Yoshioka, Shota
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supporting information
p. 1510 - 1524
(2021/06/18)
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- Preparation method of halogen-substituted alkylaniline
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The invention relates to a preparation method of halogen-substituted alkylaniline, and particularly discloses a method for obtaining halogen-substituted alkylaniline by taking alkylaniline as a raw material to react with hydrobromic acid and hydrogen peroxide in a micro-channel reactor. According to the technical scheme, by adopting the modular micro-channel reaction device, the mass transfer andheat transfer efficiency is improved, and the method has the characteristics of simplicity and safety in operation, high yield and less three wastes, and is suitable for industrial production.
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Paragraph 0034-0039; 0043-0045; 0046; 0047
(2020/05/02)
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- Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes
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The regioselective conversion of alkyl-substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N-methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one-pot procedure that includes an initial alkene hydroaminoalkylation with an α-silylated amine substrate and a subsequent protodesilylation reaction that delivers linear hydroaminoalkylation products with high selectivity from simple alkyl-substituted alkenes. For that purpose, new titanium catalysts have been developed, which are able to activate the α-C?H bond of more challenging α-silylated amine substrates. In addition, a direct relationship between the ligand structure of the new catalysts and the obtained regioselectivity is described.
- Warsitz, Michael,Doye, Sven
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supporting information
p. 15121 - 15125
(2020/10/23)
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- COMPOUNDS AND COMPOSITIONS FOR TREATING CONDITIONS ASSOCIATED WITH NLRP ACTIVITY
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In one aspect, compounds of Formula A, or a pharmaceutically acceptable salt thereof, are featured (Formula A) or a pharmaceutically acceptable salt thereof, wherein the variables shown in Formula A can be as defined anywhere herein.
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Page/Page column 332-333
(2020/06/10)
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- SULFONAMIDE DERIVATIVES AND USES THEREOF
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The present disclosure relates to compounds of Formula (I) or (II): and to their prodrugs, pharmaceutically acceptable salts, pharmaceutical compositions, methods of use, and methods for their preparation. The compounds disclosed herein are useful for inhibiting the maturation of cytokines of the IL-1 family by inhibiting inflammasomes and may be used in the treatment of disorders in which inflammasome activity is implicated, such as inflammatory, autoinflammatory and autoimmune diseases and cancers.
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Paragraph 0804; 0812
(2020/12/30)
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- Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
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Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
- Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
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supporting information
p. 1122 - 1128
(2020/03/03)
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- Photophysical processes in rhenium(I) diiminetricarbonyl arylisocyanides featuring three interacting triplet excited states
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We present a series of four transition-metal complexes based on the rhenium(I) tricarbonyl 1,10-phenanthroline (phen) template, with a lone ancillary arylisocyanide (CNAr) ligand to yield metal-organic chromophores of the generic molecular formula [Re(phen)-(CO)3(CNAr)]+ [CNAr = 2,6-diisopropylphenyl isocyanide (1), 4-phenyl-2,6-diisopropylphenyl isocyanide (2), 4-phenylethynyl-2,6-diisopropylphenyl isocyanide (3), and 4-biphenyl-2,6-diisopropylphenyl isocyanide (4)]. This particular series features varied degrees of π-conjugation length in the CNAr moiety, resulting in significant modulation in the resultant photophysical properties. All molecules possess long-lived [8- 700 μs at room temperature (RT)], strongly blue-green photoluminescent and highly energetic excited states λmax,em = 500-518 nm; Φ = 14-64%). Each of these chromophores has been photophysically investigated using static and dynamic spectroscopic techniques, the latter probed from ultrafast to suprananosecond time scales using transient absorption and photoluminescence (PL). Time-resolved PL intensity decays recorded as a function of the temperature were consistent with the presence of at least two emissive states lying closely spaced in energy with a third nonemissive state lying much higher in energy and likely ligand-field in character. The combined experimental evidence, along with the aid of electronic structure calculations (density functional theory and time-dependent density functional theory performed at the M06/Def2-SVP/SDD level), illustrates that the CNAr ligand is actively engaged in manipulating the excited-state decay in three of these molecules (2-4), wherein the triplet metal-to-ligand charge-transfer (3MLCT) state along with two distinct triplet ligand-centered (3LC) excited-state configurations (phen and CNAr) conspire to produce the resultant photophysical properties. Because the π conjugation within the CNAr ligand was extended, an interesting shift in the dominant photophysical processes was observed. When the CNAr conjugation length is short, as in 1, the phenanthroline 3LC state dominates, resulting in a configurationally mixed triplet excited state of both LC and MLCT character. With more extended π conjugation in the CNAr subunit (2-4), the initially generated 3LC(phen)/3MLCT excited state ultimately migrates to the CNAr 3LC state on the order of tens of picoseconds. Molecules 3 and 4 in this series also feature unique examples of inorganic excimer formation, as evidenced by dynamic self-quenching in the corresponding PL intensity decays accompanied by the observation of a short-lived low-energy emission feature.
- Favale, Joseph M.,Danilov, Evgeny O.,Yarnell, James E.,Castellano, Felix N.
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supporting information
p. 8750 - 8762
(2019/08/20)
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- SULPHONAMIDES AND COMPOSITIONS THEREOF FOR TREATING CONDITIONS ASSOCIATED WITH NLRP ACTIVITY
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In one aspect, compounds of Formula AA, or a pharmaceutically acceptable salt thereof, are featured: wherein the variables shown in Formula AA can be as defined anywhere herein. Compounds AA are modulators of NLRP1 and/or NLRP3
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Page/Page column 478
(2019/05/10)
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- COMPOUNDS AND COMPOSITIONS FOR TREATING CONDITIONS ASSOCIATED WITH NLRP ACTIVITY
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In one aspect, compounds of Formula AA, or a pharmaceutically acceptable salt thereof, are featured. The variables shown in Formula AA are as defined in the claims. The compounds of formula AA are NLRP3 activity modulators and, as such, can be used in the treatment of metabolic disorders (e.g. Type 2 diabetes, atherosclerosis, obesity or gout), a disease of the central nervous system (e.g. Alzheimer's disease, multiple sclerosis, Amyotrophic Lateral Sclerosis or Parkinson's disease), lung disease (e.g. asthma, COPD or pulmonary idiopathic fibrosis), liver disease (e.g. NASH syndrome, viral hepatitis or cirrhosis), pancreatic disease (e.g. acute pancreatitis or chronic pancreatitis), kidney disease (e.g. acute kidney injury or chronic kidney injury), intestinal disease (e.g. Crohn's disease or Ulcerative Colitis), skin disease (e.g. psoriasis), musculoskeletal disease (e.g. scleroderma), a vessel disorder (e.g. giant cell arteritis), a disorder of the bones (e.g. osteoarthritis, osteoporosis or osteopetrosis disorders), eye disease (e.g. glaucoma or macular degeneration), a disease caused by viral infection (e.g. HIV or AIDS), an autoimmune disease (e.g. Rheumatoid Arthritis, Systemic Lupus Erythematosus or Autoimmune Thyroiditis), cancer or aging.
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Page/Page column 445; 446; 453
(2019/02/13)
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- CATALYSTS
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A complex of formula (I) wherein M is zirconium or hafnium; each X independently is a sigma ligand; L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C20-hydrocarbyl group optionally containing one or more silicon atoms or heteroatoms of Group 14-16 of the periodic table or fluorine atoms, and optionally two R' groups taken together can form a ring; R2 and R2' are each independently a C1-C20 hydrocarbyl group, -OC1- hydrocarbyl group or -SC1-20 hydrocarbyl group; R5 is a -OC1-20 hydrocarbyl group or -SC1-20 hydrocarbyl group, said R5 group being optionally substituted by one or more halo groups; R5' is hydrogen or a C1-20 hydrocarbyl group; -OC1-20 hydrocarbyl group or -SC1-20 hydrocarbyl group; said C1-20 hydrocarbyl group being optionally substituted by one or more halo groups; R6 and R6' are each independently a C1-20 hydrocarbyl group; -OC1-20 hydrocarbyl group or -SC1-20 hydrocarbyl group; each R1 and R1' are independently -CH2Rx wherein Rx are each independently H, or a C1-20 hydrocarbyl group, optionally containing heteroatoms.
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Page/Page column 55
(2018/06/06)
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- Introducing NacNac-Like Bis(4,6-isopropylbenzoxazol-2-yl)methanide in s-Block Metal Coordination
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Within this work, the field of bulky methanides in metal coordination is exceeded by the synthesis of the versatile and promising bis(4,6-isopropylbenzoxazol-2-yl)methane (7) ligand platform. As an enhancement in this class of ligands, isopropyl (iPr) substituents as steric-demanding groups have been successfully introduced in proximity to the coordination pocket, mimicking the shielding abilities of the ubiquitous NacNac ligand scaffold to improve the steric protection of a coordinated s-block metal cation. A percent buried volume (% Vbur) calculation as well as an electronic structure analysis shades light onto the shielding and electronic abilities of the ligand in comparison to other selected methanides and diketiminates. Upon deprotonation with a variety of different group 1 and 2 metalation agents, a row of novel s-block metal complexes of the parent deprotonated monoanionic ligand 7 was obtained and structurally, as well as spectroscopically, characterized. In particular, in this context, the alkali-metal precursor complexes [Li(THF)2{(4,6-iPr-NCOC6H2)2CH}] (8) and [K{μ-(4,6-iPr-NCOC6H2)2CH}]∞ (9) as well as the alkaline-earth-metal compounds [MgCl(THF)2{(4,6-iPr-NCOC6H2)2CH}] (10) and [M(THF)n{(4,6-iPr-NCOC6H2)2CH}2] [M = Mg, n = 0 (11); M = Ca, n = 1 (12); M = Sr, n = 1 (13); M = Ba, n = 1 (14)] were successfully synthesized. Especially, the latter four exhibit interesting trends in the solid state as well as in solution within the metal series.
- Koehne, Ingo,Graw, Nico,Teuteberg, Thorsten,Herbst-Irmer, Regine,Stalke, Dietmar
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supporting information
p. 14968 - 14978
(2017/12/26)
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- A Functional Zn(II) Metallacycle Formed from an N-Heterocyclic Carbene Precursor: A Molecular Sensor for Selective Recognition of Fe3+ and IO4- Ions
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We have reported the synthesis and structural characterization of a unique Zn(II) metallacycle (1) and its utilization as a fluorescent probe for the shape-specific selective recognition (turn-off) of Fe3+ and IO4- ions. The relevant Stern-Volmer graphs indicate that the recognitions of Fe3+ and IO4- ions are examples of diphasic and monophasic quenchings, respectively. The title metallacycle has been prepared by the reaction of a novel N-heterocyclic carbene precursor, 1,3-bis(2,6-diisopropyl-4-(pyridin-4-yl)phenyl)-1H-imidazol-3-ium chloride/bromide (L), and zinc(II) chloride salt. Notably, the ligand itself did not show any type of recognition for any ions. DFT calculations were performed on L and metallacycle 1 using the geometric parameters, obtained from their single-crystal X-ray diffraction data, to understand the electronic structures of the ligand and macrocycle. The detection limit for the recognition of the Fe3+ ion was determined to be 2.5 × 10-6 mol/L, and that for IO4- ion was found to be 6.3 × 10-5 mol/L.
- Kumar, Girijesh,Guda, Ramu,Husain, Ahmad,Bodapati, Ramakrishna,Das, Samar K.
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supporting information
p. 5017 - 5025
(2017/05/08)
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- Click-binol-phosphoric acid catalysts in intramolecular enantioselective oxidative C[sbnd]H-bond functionalization
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Counteranion-catalysis represents an appealing but challenging approach for the development of enantioselective oxidative C[sbnd]H bond functionalization reactions. In this work, a new family of 3,3′-triazolyl BINOL-derived phosphoric acids was synthesized and employed in the intramolecular asymmetric C[sbnd]H bond functionalization of N-aryl substituted tetrahydroisoquinolines. As previously reported with related structures, the presence of the triazole groups on the catalysts was key to attain enantioselectivity. Our study also shows the importance of choosing the appropriate regioisomeric triazole groups at the BINOL backbone to achieve a more efficient chirality transfer. Moderate enantiomeric ratios were obtained with the N-benzamide substrates, whereas the change of the nature of the nucleophile fragment was translated to a dramatic loss of the enantioselectivity. Therefore, it can be foreseen that there is a need for designing further superior catalyst structures to develop future counter-anion organocatalyzed asymmetric C[sbnd]H bond functionalization reactions.
- Stockerl, Sebastian,Gutiérrez, Daniel,García Manche?o, Olga
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p. 572 - 585
(2016/12/16)
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- LIGHT-EMITTING COMPOUND
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A compound of formula (I): wherein M is a transition metal; x is at least 1; z is 0 or a positive integer; L1 is a ligand selected from one of ligands (II-A), (II-B); L2 is a ligand selected from another of ligands of formulae (II-A), (II-B) and (II-C); and L3 is a ligand other than a ligand of formulae (II-A), (II-B) or (II-C): (II-A) (II-B) (II-C) in which each of R1 - R6 is substituent and Ar1 - Ar3 are each an unsubstituted or substituted aryl or heteroaryl group. The compound of formula (I) may be used as a phosphorescent light-emitting material of an organic light-emitting device.
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Page/Page column 24; 27; 28
(2017/07/06)
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- Organic electroluminescent materials and devices
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Phosphorescent metal complexes comprising a pendant redox-active metallocene are disclosed. These complexes are useful as emitters for phosphorescent OLEDs.
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Page/Page column 138
(2016/10/17)
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- Ring-Closing and Cross-Metathesis with Artificial Metalloenzymes Created by Covalent Active Site-Directed Hybridization of a Lipase
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A series of Grubbs-type catalysts that contain lipase-inhibiting phosphoester functionalities have been synthesized and reacted with the lipase cutinase, which leads to artificial metalloenzymes for olefin metathesis. The resulting hybrids comprise the organometallic fragment that is covalently bound to the active amino acid residue of the enzyme host in an orthogonal orientation. Differences in reactivity as well as accessibility of the active site by the functionalized inhibitor became evident through variation of the anchoring motif and substituents on the N-heterocyclic carbene ligand. Such observations led to the design of a hybrid that is active in the ring-closing metathesis and the cross-metathesis of N,N-diallyl-p-toluenesulfonamide and allylbenzene, respectively, the latter being the first example of its kind in the field of artificial metalloenzymes.
- Basauri-Molina, Manuel,Verhoeven, Dide G. A.,Van Schaik, Arnoldus J.,Kleijn, Henk,Klein Gebbink, Robertus J. M.
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p. 15676 - 15685
(2015/11/03)
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- Bespoke photoreductants: Tungsten arylisocyanides
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Modular syntheses of oligoarylisocyanide ligands that are derivatives of 2,6-diisopropylphenyl isocyanide (CNdipp) have been developed; tungsten complexes incorporating these oligoarylisocyanide ligands exhibit intense metal-to-ligand charge-transfer visible absorptions that are red-shifted and more intense than those of the parent W(CNdipp)6 complex. Additionally, these W(CNAr)6 complexes have enhanced excited-state properties, including longer lifetimes and very high quantum yields. The decay kinetics of electronically excited W(CNAr)6 complexes (W(CNAr)6) show solvent dependences; faster decay is observed in higher dielectric solvents. W(CNAr)6 lifetimes are temperature dependent, suggestive of a strong coupling nonradiative decay mechanism that promotes repopulation of the ground state. Notably, W(CNAr)6 complexes are exceptionally strong reductants: [W(CNAr)6]+/W(CNAr)6 potentials are more negative than -2.7 V vs [Cp2Fe]+/Cp2Fe. (Figure Presented).
- Sattler, Wesley,Henling, Lawrence M.,Winkler, Jay R.,Gray, Harry B.
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p. 1198 - 1205
(2015/02/05)
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- ARGININE METHYLTRANSFERASE INHIBITORS AND USES THEREOF
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Described herein are compounds of Formula (I), pharmaceutically acceptable salts thereof, and pharmaceutical compositions thereof. Compounds described herein are useful for inhibiting arginine methyltransferase activity. Methods of using the compounds for treating arginine methyltransferase-mediated disorders are also described.
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Paragraph 0272
(2014/11/11)
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- Monofunctional hyperbranched ethylene oligomers
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The neutral κ2N,O-salicylaldiminato Ni(II) complexes [κ2N,O-{(2,6-(3′,5′-R2C 6H3)2C6H3-Ni -C(H)-(3,5-I2-2-O-C6H2)}]NiCH 3(pyridine)] (1a-pyr, R = Me; 1b-pyr, R = Et; 1c-pyr, R = iPr) convert ethylene to hyperbranched low-molecular-weight oligomers (Mn ca. 1000 g mol-1) with high productivities. While all three catalysts are capable of generating hyperbranched structures, branching densities decrease significantly with the nature of the remote substituent along Me > Et > iPr and oligomer molecular weights increase. Consequently, only 1a-pyr forms hyperbranched structures over a wide range of reaction conditions (ethylene pressure 5-30 atm and 20-70 C). An in situ catalyst system achieves similar activities and identical highly branched oligomer microstructures, eliminating the bottleneck given by the preparation and isolation of Ni-Me catalyst precursor species. Selective introduction of one primary carboxylic acid ester functional group per highly branched oligoethylene molecule was achieved by isomerizing ethoxycarbonylation and alternatively cross metathesis with ethyl acrylate followed by hydrogenation. The latter approach results in complete functionalization and no essential loss of branched oligomer material and molecular weight, as the reacting double bonds are close to a chain end. Reduction yielded a monoalcohol-functionalized oligomer. Introduction of one reactive epoxide group per branched oligomer occurs completely and selectively under mild conditions. All reaction steps involved in oligomerization and monofunctionalization are efficient and readily scalable.
- Wiedemann, Thomas,Voit, Gregor,Tchernook, Alexandra,Roesle, Philipp,Goettker-Schnetmann, Inigo,Mecking, Stefan
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supporting information
p. 2078 - 2085
(2014/03/21)
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- Donor-substituted distyrylpyrazines: Influence of steric congestion on UV-Vis absorption and fluorescence
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Di(p-aminostyryl)pyrazines with voluminous substituents on the nitrogen and in the adjacent positions were prepared via twofold aldol condensation. Absorption and emission spectra are influenced by increasing steric hindrance because the orbital overlap between nitrogen and π-system is modulated by voluminous groups. Strong solvatochromism of the fluorescence and huge Stokes shifts result from amplified donor-acceptor interaction in the excited state. Protonation occurs at the terminal amino groups first, followed by protonation of the central pyrazine. With increasing strength of acid, absorption and emission spectra are first shifted to the blue followed by a redshift. Copyright
- Wink, Christoph,Detert, Heiner
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supporting information
p. 144 - 150
(2013/03/13)
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- Scope and mechanism of the Pt-catalyzed enantioselective diboration of monosubstituted alkenes
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The Pt-catalyzed enantioselective diboration of terminal alkenes can be accomplished in an enantioselective fashion in the presence of chiral phosphonite ligands. Optimal procedures and the substrate scope of this transformation are fully investigated. Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining step in the catalytic cycle is olefin migratory insertion into a Pt-B bond. Density functional theory analysis, combined with other experimental data, suggests that the insertion reaction positions platinum at the internal carbon of the substrate. A stereochemical model for this reaction is advanced that is in line both with these features and with the crystal structure of a Pt-ligand complex.
- Coombs, John R.,Haeffner, Fredrik,Kliman, Laura T.,Morken, James P.
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supporting information
p. 11222 - 11231
(2013/08/23)
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- NOVEL TETRADENTATE PLATINUM COMPLEXES
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Novel phosphorescent tetradentate platinum (II) compounds comprising a twisted aryl group are provided. Also provided are novel phosphorescent tetradentate platinum (II) compounds comprising an imidazo[1,2-f]phenanthridine moiety. The compounds may be used in organic light emitting devices to provide improved device efficiency, line shape and lifetime.
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Page/Page column 120
(2012/09/11)
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- PYRROLO SULFONAMIDE COMPOUNDS FOR MODULATION OF ORPHAN NUCLEAR RECEPTOR RAR-RELATED ORPHAN RECEPTOR-GAMMA (RORGAMMA, NR1F3) ACTIVITY AND FOR THE TREATMENT OF CHRONIC INFLAMMATORY AND AUTOIMMUNE DISEASES
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The invention provides modulators for the orphan nuclear receptor RORy and methods for treating RORy mediated diseases by administrating these novel RORy modulators to a human or a mammal in need thereof. Specifically, the present invention provides pyrrolo sulfonamide compounds of Formula (1) and the enantiomers, diastereomers, tautomers, solvates and pharmaceutically acceptable salts thereof.
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Page/Page column 47
(2012/11/06)
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- Catalytic enantioselective 1,2-diboration of 1,3-dienes: Versatile reagents for stereoselective allylation
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More with boron: The development of catalytic enantioselective 1,2-diboration of 1,3-dienes enables a new strategy for enantioselective carbonyl allylation reactions (see scheme). These reactions occur with outstanding levels of stereoselection and can be applied to both monosubstituted and 1,1-disubstituted dienes. The carbonyl allylation reactions provide enantiomerically enriched functionalized homoallylic alcohol products. Copyright
- Kliman, Laura T.,Mlynarski, Scott N.,Ferris, Grace E.,Morken, James P.
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supporting information; experimental part
p. 521 - 524
(2012/03/11)
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- Synthesis, photophysical properties, and molecular aggregation of gold(I) complexes containing carbon-donor ligands
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A series of gold(I) complexes with N-heterocyclic carbene (NHC) and acetylide ligands, namely [Au(NHC1)(C≡CAr)] (NHC 1=1-(9-anthracenylmethyl)-3-(n)-butylimidazol-2-ylidene; 1b-1g), [Au(NHC2)(C≡CAr)] (NHC2=1,3-diethylimidazol-2- ylidene; 2b-2f) and [Au(C≡NAr)2]+ (C≡NAr=arylisocyanide; 3a-3f) have been synthesized. At room temperature, most of these gold(I) complexes are emissive in the solid state and in solutions with lifetimes in the nanosecond to submicrosecond regime. The emissions of complexes 1b-1g in solutions are assigned to 1π-π* excited states of the NHC ligand, while that of 2b-2f and 3a-3f are phosphorescent in nature. The intriguing solvatochromism of complex 3a was also investigated. Complexes 1b, 1d, 3a, and 3e aggregate into crystalline nanowires in freshly prepared THF/water dispersions. The X-ray crystallographic data reveal that 1b and 1d possess intermolecular π-π and C-H ... π interactions; while 3a was found to display intermolecular gold(I) ... π interactions. Copyright
- Chow, Andy Lok-Fung,So, Man-Ho,Lu, Wei,Zhu, Nianyong,Che, Chi-Ming
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supporting information; experimental part
p. 544 - 553
(2011/10/12)
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- Synthesis and photoinitiating properties of N-substituted 2,6-diisopropylanilines
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Reactions of 2,6-diisopropylaniline and its 4-bromo and 4-thiocyanato derivatives with methyl iodide in dimethylformamide in the presence of potassium carbonate gave exclusively the corresponding N,N-dimethyl-substituted products. Heating of 2,6-diisopropylaniline and 2,6-diisopropyl-4-thiocyanatoaniline with methyl iodide without a solvent afforded only N-methyl derivatives. Pleiades Publishing, Ltd., 2011.
- Kolchina,Shekleina,Shelkovnikov
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experimental part
p. 855 - 861
(2011/10/02)
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- NOVEL RAR RECEPTOR AGONIST LIGANDS AND USE THEREOF IN HUMAN MEDICINE AND COSMETICS
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The invention relates to compounds corresponding to general formula (I) below: to the compositions containing same, to methods for the preparation thereof and to the use thereof in pharmaceutical compositions for use in human or veterinary medicine, or else in cosmetic compositions.
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Page/Page column 8
(2010/11/03)
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- DIPHOSPHINE LIGAND AND TRANSITION METAL COMPLEX USING THE SAME
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The present invention provides a novel ligand represented by the following formula and a novel transition metal complex having the ligand, which shows superior enantioselectivity and catalytic efficiency, particularly high catalyst activity, in various asymmetric synthesis reactions. A transition metal complex having, as a ligand, a compound represented by the formula wherein R4 is a hydrogen atom or a C1-6 alkyl group optionally having substituent(s), and R5 and R6 are each a C1-6 alkyl group optionally having substituent(s), or the formula is a group represented by the formula wherein ring B is a 3- to 8-membered ring optionally having substituent (s).
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Page/Page column 24-25
(2008/12/06)
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- HALOGEN SUBSTITUTED METALLOCENE COMPOUNDS FOR OLEFIN POLYMERIZATION
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A metallocene compound is represented by the formula (1): AMXn-1 wherein M is a transition metal atom having a coordination number of n selected from Group 3, 4, 5 or 6 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom; A is a substituted monocyclic or polycyclic arenyl ligand pi-bonded to M, wherein said arenyl ligand includes at least one halogen substituent directly bonded to any sp2 carbon atom at a bondable ring position of the ligand; and the or each X is a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
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Page/Page column 111
(2010/11/27)
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- Halogen substituted metallocene compounds for olefin polymerization
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A metallocene compound is represented by the formula (1): [in-line-formulae]AMXn-1 [/in-line-formulae]wherein M is a transition metal atom having a coordination number of n selected from Group 3, 4, 5 or 6 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom; A is a substituted monocyclic or polycyclic arenyl ligand pi-bonded to M, wherein said arenyl ligand includes at least one halogen substituent directly bonded to any sp2 carbon atom at a bondable ring position of the ligand; and the or each X is a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
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- Syntheses of sterically hindered pyridinium phenoxides as model compounds in nonlinear optics
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Noncentrosymmetric molecules with a π-conjugated system and, among them, push-pull molecules such as pyridinium phenoxide, are a promising new class of materials for applications in optoelectronics due to their nonlinear optical (NLO) properties. Modelling studies have indicated that an increase in the twist angle between the two aromatic rings leads to an enhancement of the NLO properties. In order to confirm this feature experimentally, it was necessary to prepare a series of new hindered pyridinium phenoxides. Their efficient syntheses by Suzuki cross-coupling reactions are described herein. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Diemer, Vincent,Chaumeil, Helene,Defoin, Albert,Fort, Alain,Boeglin, Alex,Carre, Christiane
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p. 2727 - 2738
(2007/10/03)
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- Polymer-supported chiral Schrock catalysts immobilized via the arylimido ligand
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The immobilization of both chiral and non-chiral versions of the Schrock catalyst via the arylimido ligand was accomplished for the first time. For this purpose, four different 4-(6-halogenohexyl)-2,6-R2-anilines, i.e., {4-[6-X-(CH2)6]-2,6-R2-C6H 2-NH2} (7: R = Me, X = Br; 8: R = Me, X = Cl, 9: R = 2-Pr, X = Cl, 10: R = 2-Pr, X = Br) were prepared and used for the synthesis of the corresponding Mo-bis(imido)dichloro complexes Mo{N-2,6-R2-4-[6-X- (CH2)6]-C6H2)2Cl 2-DME (11: R = Me, X = Br; 12: R = Me, X = Cl; 13: R = 2-Pr, X = Cl; 14: R = 2-Pr, X = Br). Compounds 11-14 were transformed into the corresponding Mo-bis(imido)dialkyl complexes Mo{N-2,6-R2-4-[6-X-(CH 2)6]-C6H2}2(CH 2CMe2Ph)2 (15: R = Me, X = Br; 16: R = Me, X = Cl, 17: R = 2-Pr, X = Cl; 18: R = 2-Pr, X = Br). These were used for the synthesis of the Mo-imidoalkylidene triflates Mo{N-2,6-R2-4-[6-X- (CH2)6]-C6H2}(CHCMe 2Ph)-(OTf)2·DME (19: R = Me, X = Br; 20: R = 2-Pr, X = Br, 21: R = 2-Pr, X = Cl). Compounds 19-21 were used in the synthesis of the Schrock type catalysts Mo{N-2,6-Me2-4-[6-Br-(CH2) 6]-C6H2} (CHCMe2Ph)[OC(CH 3)(CF3)2]2 (22) and Mo{N-2,6-(2-Pr)24-[6-Cl-(CH2)6]-C 6H2}(CHCMe2Ph)[OC-(CH3)(CF 3)2] (23), Mo{N-2,6-Me2-4-[6-Br-(CH 2)6]-C6H2}(CHCMe2Ph)[(R)- BIPHEN] (24) and Mo{N-2,6-(2-Pr)2-4-[6-Br-(CH2) 6]-C6H2}(CHCMe2Ph)[(R)-BIPHEN] (25). Compounds 22, 24 and 25 were immobilized on Ag-perfluoroalkylsulfonate-modified PS- and PS-DVB materials to yield the corresponding immobilized catalysts Mo{N-2,6-Me2-4-[PS-CH2-O-CF2-CF(CF 3)-SO3-(CH2)6]-C6H 2}(CHCMe2Ph)-[OCMe(CF3)2] 2 (26), Mo{N-2,6-Me2-4-[PS-DVB-CH2-O-CF 2-CF(CF3)-SO3-(CH2) 6]-C6H2} (CHCMe2Ph)[(R)-BIPHEN] (27) Mo{N-2,6-(2-Pr)2-4-[PS-DVB-CH2-O-CF2- CF(CF3)-SO3-(CH2)6]-C 6H2) (CHCMe2Ph)[(R)-BIPHEN] (28). These were used in a series of ring-closing metathesis (RCM), ring-opening cross metathesis, asymmetric RCM and desymmetrization reactions. The use of 27 and 28 resulted in values for enantiomeric excess (ee) virtually identical to those obtained with the corresponding homogeneous chiral catalysts.
- Wang, Dongren,Kroell, Roswitha,Mayr, Monika,Wurst, Klaus,Buchmeiser, Michael R.
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p. 1567 - 1579
(2007/10/03)
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- Efficient slurry-phase homopolymerization of ethylene to branched polyethylenes using α-diimine nickel(II) catalysts covalently linked to silica supports
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α-Diimine nickel(II) complexes covalently linked to a silica support were obtained by the reaction of an amino- or hydroxy-functionalized α-diimine nickel complex with silica particles treated with trimethyl aluminum. These silica-supported aryl α-diimine nickel(II) precatalysts linked via an amino (1a) or hydroxy functionality (1b-c) at the p-aryl position, and precatalysts linked via one (2a) or two (2b) hydroxy functionalities in the alkyl backbone were used in slurry polymerizations of ethylene to produce branched polyethylenes. Activation of precatalysts with ethylaluminum sesquichloride was effective even at very low Al/Ni ratios of 48. Initial polymerizations, performed at 60°C and 150 psig ethylene, showed excellent productivities of up to 10.8 kg PE per gram of 1b (3.0 wt % nickel loading). Low productivities at temperatures above 60°C can in part be overcome by increase in ethylene pressure. For example, a productivity of 6.0 kg PE per gram of 1b (3.0 wt% nickel loading) was obtained at 80°C and 700 psig ethylene. The best polymerization productivities were obtained with trimethylalumlnum as a traceless silica-linker, however, tetrachlorosilane and trichloroborane are attractive alternatives. Branching densities can be controlled by choice of ortho-aryl substituents. No reactor fouling occurs with these supported catalysts.
- Schrekker, Henri S.,Kotov, Vasily,Preishuber-Pflugl, Peter,White, Peter,Brookhart, Maurice
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p. 6341 - 6354
(2007/10/03)
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- Highly active new α-diimine nickel catalyst for the polymerization of α-olefins
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A new silylated α-diimine ligand, bis[N,N′-(4-tert-butyl- diphenylsilyl-2,6-diisopropylphenyl)imino]acenaphthene 3, and its corresponding Ni(II) complex, {bis[N,N′-(4-tert-butyl-diphenylsilyl-2,6- diisopropylphenyl)imino]acenaphthene}dibromonickel 4, have been synthesized and characterized. The crystal structures of 3 and 4 were determined by X-ray crystallography. In the solid state, complex 4 is a dimer with two bridging Br ligands linking the two nickel centers, which have square pyramidal geometries. Complex 4, activated either by diethylaluminum chloride (DEAC) or methylaluminoxane (MAO) produces very active catalyst systems for the polymerization of ethylene and moderately active for the polymerization of propylene. The activity values are in the order of magnitude of 107 g PE (mol Ni [E] h)-1 for the polymerization of ethylene and of 105 g PP (mol Ni [P] h)-1 for the polymerization of propylene. NMR analysis shows that branched polyethylenes (PE) are obtained at room or higher temperatures and almost linear PE is obtained at 0°C with 4/DEAC.
- Liu, Hua-Rong,Gomes, Pedro T.,Costa, Sandra I.,Duarte, M. Teresa,Branquinho,Fernandes, Anabela C.,Chien, James C.W.,Singh,Marques, Maria M.
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p. 1314 - 1323
(2007/10/03)
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- Fe(II) and Co(II) pyridinebisimine complexes bearing different substituents on ortho- and para-position of imines: Synthesis, characterization and behavior of ethylene polymerization
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A series of 2,6-bis(imino)pyridyl iron(II) and cobalt(II) complexes [2,6-(ArNCMe)2C5H3N]MCl2 (Ar = 2,6-i-Pr2C6H3, M = Fe: 3a, M = Co: 4a; Ar = 2,4,6-i-Pr3C6H2, M = Fe: 3b, M = Co: 4b; Ar = 2,6-i-Pr2-4-BrC6H2, M = Fe: 3c, M = Co: 4c; Ar = 2,4-i-Pr2-6-BrC6H2, M = Fe: 3d, M = Co: 4d) has been synthesized, characterized, and investigated as precatalysts for the polymerization of ethylene in the presence of modified methylaluminoxane (MMAO). The substituents of pyridinebisimine ligands and their positions located significantly influence catalyst activity and polymer property. It is found that the catalytic activities of the iron complexes/MMAO systems are mainly dominated by electronical effect, while those of the cobalt complexes/MMAO systems are primarily controlled by hindering effect.
- Liu, Jing-Yu,Zheng, Yi,Li, Yan-Guo,Pan, Li,Li, Yue-Sheng,Hu, Ning-Hai
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p. 1233 - 1239
(2007/10/03)
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- SYNTHESIS OF PERYLENE-PORPHYRIN BUILDING BLOCKS AND POLYMERS THEREOF FOR THE PRODUCTION OF LIGHT-HARVESTING ARRAYS
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The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula (I): wherein m is at least 1; X1 is a charge separation group, and X2 through Xm+1 are chromophores. At least one of X2 through Xm+1 has at least one perylene group coupled thereto.
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- Transformation of mutagenic aromatic amines into non-mutagenic species by alkyl substituents: Part I. Alkylation ortho to the amino function
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Alkyl-substituted derivatives of 2-aminonaphthalene (2-AN) 1, 2-aminofluorene (2-AF) 6 and 4-aminobiphenyl (4-ABP) 11 were synthesized and the mutagenic activity of these compounds determined in Salmonella typhimurium strains TA98 and TA100 with and without S9 mix. In the case of the ortho-substituted 4-aminobiphenyls 12-15 (3-alkyl = ethyl, iso-propyl, n-butyl, tert-butyl) the substituent with the strongest steric demand (3-tert-butyl) shows the strongest influence on the decrease of mutagenicity if compared with the parent compound. In the series of the bis-ortho-disubstituted compounds 16-18 (3,5-dimethyl-, 3,5-diethyl- and 3,5-diisopropyl-4-aminobiphenyl) generation of non-mutagenic species occurs already with the introduction of two ethyl groups. For the 4-aminobiphenyl derivatives 12-15 and 16-18, as well as for the 1-alkylated 2-aminofluorenes 7-10 and the 1-alkylated 2-aminonaphthalenes 2-5 a smaller mutagenicity was observed if compared with predicted mutagenicities as calculated by the QSAR equations of Debnath et al. (Environ. Mol. Mutagen. 19 (1992) 37). The largest differences resulted in the cases of the tert-butyl substituted compounds. Only with smaller alkyl groups like ethyl the QSAR predictions and the experimentally determined mutagenicities come close to each other. Thus, these results show that appropriate alkyl substitution reduces (eliminates) mutagenicity, secondly, it is necessary to introduce steric parameters to predict the mutagenicity of such compounds correctly.
- Glende, Carsten,Schmitt, Heimo,Erdinger, Lothar,Engelhardt, Guenter,Boche, Gernot
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- Ligand variation in alkylidene complexes of the type Mo(CHR)(NR')(OR'')2
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A variety of complexes of the type Mo(NR)2Cl2L2 (R=4-Br-2,6-i-Pr2-C6H2, 4-CN-2,6-i-Pr2-C6H2, 3,5-Me2-C6H3, 2-i-Pr-C6H4, 2-CF3-C6H4, 2-Ph-C6H4, and 1-adamantyl; L=1/2 DME or pyridine) have been synthesized by treating 2 with four equivalents of RNH2 in the presence of Me3SiCl and Et3N.They are readily alkylated by Grignard reagents to give complexes of the type Mo(NR)2(CH2R')2 (R=4-Br-2,6-i-Pr2-C6H2, 4-CN-2,6-i-Pr2-C6H2, 2,6-Me2-C6H3, 3,5-Me2-C6H3, 2-t-Bu-C6H4, 2-i-Pr-C6H4, 2-CF3-C6H4, 2-Ph-C6H4, 1-adamantyl, R'=t-Bu or PhMe2C) from which alkylidene complexes of the type Mo(NR)(CHR')(OTf)2(DME) are formed upon addition of triflic acid.Addition of various alkoxides to the triflate complexes yields four-coordinate complexes of the type Mo(NR)(CHR')(OR'')2 (combinations include R=2,6-i-Pr2-C6H3, 4-Br-2,6-iPr2-C6H2, 4-CN-2,6-i-Pr2-C6H2, 2,6-Me2-C6H3, 3,5-Me2-C6H3, 2-t-Bu-C6H4, 2-i-Pr-C6H4, 2-CF3-C6H4, 2-Ph-C6H4, and 1-adamantyl; OR''=OCMe3, OCEt3, O-1-adamantyl, OCHMe2, OCMe2(CF3), OCMe(CF3)2, OC(CF3)3, and OC(CF3)2CF2CF2CF3).
- Oskam, John H.,Fox, Harold H.,Yap, Kimo B.,McConville, David H.,O'Dell, Richard,et al.
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p. 185 - 198
(2007/10/02)
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- Revisitation of Formaldehyde Aniline Condensation. VIII. - Monomeric N-Methylene Anilines
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A convenient, high yield "dry" method of synthesis of monomeric N-methyleneanilines (6a-i) and the characterization of the products by m.s., 1H- and 13C-n.m.r. and i.r. are reported, improving previous procedures and describing new compounds.It appeared that the existence of monomeric N-methyleneanilines is stricly related to the presence of enough steric hindrance to oligomerization by substituents in ortho positions.Moreover, some addition products of formaldehyde to an amine and its corresponding imines are tentatively identified on the basis of the observed mass spectrum of the whole reaction mixture.The reaction products of formaldehyde with 2,6-dimethylaniline (1a) provided an example of a mobile equilibrium between monomeric and trimeric imine.
- Giumanini, Angelo G.,Verardo, Giancarlo,Polana, Marco
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p. 161 - 174
(2007/10/02)
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- Aniline intermediates
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There are provided novel substituted aniline intermediates, useful in the synthesis of certain substituted N-nitroanilines or salts thereof which may be used to elicit several desirable and advantageous biological responses in plants.
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