110-94-1Relevant articles and documents
Visible photorelease of liquid biopsy markers following microfluidic affinity-enrichment
Brown, Virginia,Digamber, Rane,Givens, Richard S.,Jackson, J. Matt,Pahattuge, Thilanga N.,Perera, Chamani,Peterson, Blake R.,Soper, Steven A.,Wijerathne, Harshani,Witek, Malgorzata A.
, p. 4098 - 4101 (2020)
We detail a heterobifunctional, 7-aminocoumarin photocleavable (PC) linker with unique properties to covalently attach Abs to surfaces and subsequently release them with visible light (400-450 nm). The PC linker allowed rapid (2 min) and efficient (>90%) release of CTCs and EVs without damaging their molecular cargo.
Cason et al.
, p. 289,290,297 (1959)
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Dox,Yoder
, p. 649 (1922)
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Tungsten doped mesoporous SBA-16 as novel heterogeneous catalysts for oxidation of cyclopentene to glutaric acid
Jin, Manman,Zhang, Guodi,Guo, Zhenmei,Lv, Zhiguo
, (2018)
Novel heterogeneous tungsten species in mesoporous silica SBA-16 catalysts based on ship-in-a-bottle methodology are originally reported for oxidizing cyclopentene (CPE) to glutaric acid (GAC) using hydrogen peroxide (H2O2). For all W-SBA-16 catalysts, isolated tungsten species and octahedrally coordinated tungsten oxide species are observed while WO3 crystallites are detected for the W-SBA-16 catalysts with Si/ W = 5, 10, and 20. The specific surface areas and the corresponding total pore volumes decrease significantly as increasing amounts of tungsten incorporated into the pores of SBA-16. Using tungsten-substituted mesoporous SBA-16 heterogeneous catalysts, high yield of GAC (55%) is achieved with low tungsten loading (for Si/W = 30, ~13?wt%) for oxidation of CPE. The W-SBA-16 catalysts with Si/W = 30 can be reused five times without dramatic deactivation. In fact, low catalytic activity provided by bulk WO3 implies that the highly distributed tungsten species in SBA-16 and the steric confinement effect of SBA-16 are key elements for the outstanding catalytic performance.
Enantiotopically Selective Oxidation of α,ω-Diols with the Enzyme Systems of Microorganisms
Ohta, Hiromichi,Tetsukawa, Hatsuki,Noto, Naoko
, p. 2400 - 2404 (1982)
Gluconobacter were found to be capable of oxidizing prochiral diols such as 2-substituted propane-1,3-diols 1 and 3-substituted pentane-1,5-diols 4 with distinction of pro-R and pro-S sites of the molecules, in that (-)-(R)-α-substituted β-hydroxypropionic acids 2 and (+)-(3S)-3-substituted δ-valerolactones 5 were obtained, respectively.Oxidation of 3-methylpentane-1,3,5-triol 11 afforded unnatural (+)-(S)-mevalonolactone 12.The steric bulkiness of the substituents on the prochiral center and the distance from the hydroxy group greatly affected the rate and the enantioselectivity of the reaction.
MIL-101 metal-organic framework: A highly efficient heterogeneous catalyst for oxidative cleavage of alkenes with H2O2
Saedi, Zahra,Tangestaninejad, Shahram,Moghadam, Majid,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
, p. 18 - 22 (2012)
In the present work, a new and efficient method for direct oxidation of alkenes to carboxylic acids with H2O2 catalyzed by metal-organic framework MIL-101 is reported. In this transformation, the MIL-101 catalyzes the oxidation reactions by framework nodes and acts as a heterogeneous and reusable catalyst. The structure of MIL-101 was stable after three catalytic cycles.
Efficient synthesis of glutaric acid from L-glutamic acid via diazoniation/hydrogenation sequence
Zhang, Wei,Rao, Meng-Yun,Cheng, Zhong-Jun,Zhu, Xiao-Yan,Gao, Kai,Yang, Jian,Yang, Bo,Liao, Xia-Li
, p. 716 - 721 (2015)
The practical synthetic preparation of glutaric acid has remained a major challenge to date. In the present study, glutaric acid was synthesised by way of one-pot diazoniation/hydrogenation of the readily available L-glutamic acid under aqueous conditions on a gram-scale with good yields. This is the first example of the deamination of the aliphatic primary amine via diazoniation and could afford a practical approach to the production of glutaric acid.
Oxidation of Cyclopentene by RuCl3-NaOCl Catalyst
Orita, Hideo,Hayakawa, Takashi,Takehira, Katsuomi
, p. 2637 - 2638 (1986)
Oxidation of cyclopentene by RuCl3-NaOCl catalyst in an aqueous-organic two phase system was investigated by changing compositions of solvent system and additives to the aqueous solution.Use of acetonitrile as a cosolvent enhanced the reaction rate greatly, and addition of NaOH improved the yield of glutaric acid up to 80percent.
Novel photochemical reactions of carbocyclic diazodiketones without elimination of nitrogen – a suitable way to N-hydrazonation of C–H-bonds
Rodina, Liudmila L.,Azarova, Xenia V.,Medvedev, Jury J.,Semenok, Dmitrij V.,Nikolaev, Valerij A.
, p. 2250 - 2258 (2018)
The sensitized photoexcitation of 2-diazocyclopentane-1,3-diones in the presence of THF leads to the insertion of the terminal N-atom of the diazo group into the α-С–Н bond of THF, producing the associated N-alkylhydrazones in yields of up to 63–71%. Further irradiation of hydrazones derived from furan-fused tricyclic diazocyclopentanediones culminates in the cycloelimination of furans to yield 2-N-(alkyl)hydrazone of cyclopentene-1,2,3-trione. By contrast, the direct photolysis of carbocyclic diazodiketones gives only Wolff rearrangement products with up to 90–97% yield.
Oxidative cleavage of 1,3-dicarbonyls to carboxylic acids with oxone
Ashford,Grega
, p. 1523 - 1524 (2001)
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Farrar
, p. 1708 (1957)
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Osmium tetroxide-promoted catalytic oxidative cleavage of olefins: An organometallic ozonolysis
Travis, Benjamin R.,Narayan, Radha S.,Borhan, Babak
, p. 3824 - 3825 (2002)
A mild, organometallic alternative to ozonolysis utilizing oxone and OsO4 is presented. This is a direct oxidation of olefins via the carbon-carbon cleavage of an osmate ester by the action of oxone. Twenty-four different olefins were converted to their corresponding ketones or carboxylic acids in high yields (> 80%). Free alcohols, acetate- and benzyl-protected alcohols, and 1,2-diols were stable under these conditions. This method should be applicable for traditional organic synthesis. Copyright
Alkene and alkyne oxidative cleavage catalyzed by RuO4 in environmentally acceptable solvents
Griffith, William P.,Kwong, Eugene
, p. 2945 - 2951 (2003)
The application of CCl4, C6Hl2, EtOAc, and Me2CO as solvents for biphasic systems has been compared for oxidative cleavage of alkenes and alkynes by RuO4 to carboxylic acids, using the RuCl3·nH2O-IO(OH)5 reagent for which an improved procedure is described. Cyclohexane is an effective and economic replacement for the environmentally unfriendly CCl 4; acetone and ethyl acetate are less effective.
Role of added chloride ions in alteration of reaction pathway in the oxidation of cyclic ketones by dichloroisocyanuric acid - A kinetic study
Lakshman Kumar,Venkata Nadh,Radhakrishnamurti
, p. 376 - 383 (2015)
Effect of added chloride ions on kinetics and pathway of reaction between cyclic ketones (five to eight membered rings) and dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid - perchloric acid medium. Formation of aliphatic dicarboxylic acids as the end products demonstrates the ring cleavage oxidation. Positive effect of acid and negative effect of dielectric constant on the reaction rate reveals a interaction between positive ion (oxidant in the form of H2OCl+) and dipolar substrate molecule. Zero and first orders by oxidant in absence and presence of added chloride ions illustrates the participation of substrate as enolic form of ketone and protonated ketone, respectively, in the rate determining steps. The observed order of reactivity of cyclic ketones (cyclohexanone > cyclooctanone > cyclopentanone > cycloheptanone) was explained on the bases of ring strain, change of hybridization and conformational considerations. The envisaged plausible mechanism based on order of reactants in presence and absence of added chloride ions was substantiated by the order of Arrhenius parameters.
Effects of counter cations in selective monohydrolyses of symmetric diesters
Niwayama, Satomi,Rimkus, Audrius
, p. 498 - 500 (2005)
Monohydrolyses of symmetric diesters were carried out using several aqueous inorganic bases, LiOH, NaOH, KOH, and CsOH. The more reactive bases showed higher selectivities in the monohydrolyses of acyclic symmetric diesters.
Kinetics of Electron Transfer from Cyclic Ketones to Ni(IV) Periodate Complex in Aqueous Alkaline Medium
Khan, Jaffar Ali,Chandraiah, U.,Kumar, B. Kishore,Kandlikar, Sushama
, p. 1300 - 1303 (1989)
The kinetics of electron transfer from cyclic ketones (represented by (S)) to Ni(IV) periodate complexes has been studied in aqueous alkaline medium.The kinetics exhibit a pseudo-first-order disappearance of Ni(IV) periodate complexes when the is present in excess.The pseudo-first-order rate constants kobs, were linearly dependent on and the order is were found to be unity.The rate of the reaction increased with the increase in ->, however the rates were retarded with the increase in .Salt and solvent effect studies indicate that the reaction is of ion-dipole type.A suitable mechanism involving slow adduct formation between anol and oxidant, and its decomposition in a fast step have been suggested.A rate law consistent with the proposed mechanism has also been derived.The products of oxidation were identified as corresponding decarboxylic acids.
Efficient oxidative cleavage of 1,3-dicarbonyl derivatives with hydrogen peroxide catalyzed by quaternary ammonium iodide
Yuan, Yu,Ji, Xiang,Zhao, Dongbo
, p. 5274 - 5278 (2010)
Quaternary ammonium iodide, a metal-free and mild catalyst, was proven to be a successful catalyst in the oxidative cleavage of 1,3-dicarbonyl derivatives with H2O2 as terminal oxidant. The mechanistic aspects of these "multistep" catalytic oxidations were discussed in terms of the catalytic cycle of the iodine species and the oxidative cleavage of the α carbon from the dicarbonyl compounds to generate the corresponding carboxylic acids.
A Convenient Synthesis of Cyclobutanone
Seetz, J. W. F. L.,Tol, R.,Akkerman, O. S.,Bickelhaupt, F.
, p. 721 (1983)
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Automated on-line monitoring of the TiO2-based photocatalytic degradation of dimethyl phthalate and diethyl phthalate
Salazar-Beltrán, Daniel,Hinojosa-Reyes, Laura,Maya-Alejandro, Fernando,Turnes-Palomino, Gemma,Palomino-Cabello, Carlos,Hernández-Ramírez, Aracely,Guzmán-Mar, Jorge Luis
, p. 863 - 870 (2019)
A fully automated on-line system for monitoring the TiO2-based photocatalytic degradation of dimethyl phthalate (DMP) and diethyl phthalate (DEP) using sequential injection analysis (SIA) coupled to liquid chromatography (LC) with UV detection was proposed. The effects of the type of catalyst (sol-gel, Degussa P25 and Hombikat), the amount of catalyst (0.5, 1.0 and 1.5 g L-1), and the solution pH (4, 7 and 10) were evaluated through a three-level fractional factorial design (FFD) to verify the influence of the factors on the response variable (degradation efficiency, %). As a result of FFD evaluation, the main factor that influences the process is the type of catalyst. Degradation percentages close to 100% under UV-vis radiation were reached using the two commercial TiO2 materials, which present mixed phases (anatase/rutile), Degussa P25 (82%/18%) and Hombikat (76%/24%). 60% degradation was obtained using the laboratory-made pure anatase crystalline TiO2 phase. The pH and amount of catalyst showed minimum significant effect on the degradation efficiencies of DMP and DEP. Greater degradation efficiency was achieved using Degussa P25 at pH 10 with 1.5 g L-1 catalyst dosage. Under these conditions, complete degradation and 92% mineralization were achieved after 300 min of reaction. Additionally, a drastic decrease in the concentration of BOD5 and COD was observed, which results in significant enhancement of their biodegradability obtaining a BOD5/COD index of 0.66 after the photocatalytic treatment. The main intermediate products found were dimethyl 4-hydroxyphthalate, 4-hydroxy-diethyl phthalate, phthalic acid and phthalic anhydride indicating that the photocatalytic degradation pathway involved the hydrolysis reaction of the aliphatic chain and hydroxylation of the aromatic ring, obtaining products with lower toxicity than the initial molecules.
Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures.
Low, Choon Heng,Nobbs, James D.,Van Meurs, Martin,Stubbs, Ludger P.,Drent, Eite,Aitipamula, Srinivasulu,Pung, Michelle H. L.
, p. 4281 - 4292 (2015)
A series of sterically bulky diphosphines have been prepared, including P2 = trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane (4), (2-methylenepropane-1,3-diyl)bis(di-tert-butylphosphine) (5), bis[(di-tert-butylphosphino)methyl]dimethylsilane (6), and cis- and trans-11,12-bis[(di-tert-butylphosphino)methyl]-9,10-dihydro-9,10-ethanoanthracene (10 and 11). The corresponding palladium complexes of these ligands, P2Pd(CF3CO2)2, have been synthesized and characterized. The solid-state structures of [Pd(4)(CF3CO2)2], [Pd(5)(CF3CO2)2], [Pd(6)(CF3CO2)2], and [Pd(11)(CF3CO2)2] were obtained by single-crystal X-ray diffraction and confirm the bidentate binding mode of the ligand and a square-planar coordination geometry with a minor distortion from the ideal. The diphosphines in combination with Pd(OAc)2 have been applied in the hydroxycarbonylation of a mixture of pentenoic acid isomers to produce adipic acid with high selectivity (in several cases >95%). The (regio)selectivity of the hydroxycarbonylation reaction is highly dependent on the P2 diphosphine ligand structure, particularly the steric bulk of the substituents on the diphosphine donor and the P-Pd-P bite angle in the complexes, with respectively tertiary alkyl phosphine substituents (tert-butyl, adamantyl) and a C4 backbone P-Pd-P bite angle >100° being the common features of highly adipic acid selective systems. It is suggested that the regioselectivity of hydroxycarbonylation becomes largely driven by the chelation of the carboxylic acid functionality of pentenoic acid substrates, when smaller size P substituents and/or when P2 ligands with smaller bite angles (100°) are applied.
An efficient method for the catalytic aerobic oxidation of cycloalkanes using 3,4,5,6-Tetrafluoro-N-Hydroxyphthalimide (F4-NHPI)
Guha, Samar K.,Ishii, Yasutaka
, p. 327 - 335 (2021/12/13)
N-Hydroxyphthalimide (NHPI) is known to be an effective catalyst for the oxidation of hydrocarbons. The catalytic activity of NHPI derivatives is generally increased by introducing an electron-withdrawing group on the benzene ring. In a previous report, two NHPI derivatives containing fluorinated alkyl chain were prepared and their catalytic activity was investigated in the oxidation of cycloalkanes. It was found that the fluorinated NHPI derivatives showed better yields for the oxidation reaction. As a continuation of our work with fluorinated NHPI derivatives, our next aim was to investigate the catalytic activity of the NHPI derivatives by introducing fluorine atoms in the benzene ring of NHPI. In the present research, 3,4,5,6-Tetrafluoro-N-Hydroxyphthalimide (F4-NHPI) is prepared and its catalytic activity has been investigated in the oxidation of two different cycloalkanes for the first time. It has been found that F4-NHPI showed higher catalytic efficiency compared with that of the parent NHPI catalyst in the present reactions. The presence of a fluorinated solvent and an additive was also found to accelerate the oxidation.
Identification of key oxidative intermediates and the function of chromium dopants in PKU-8: catalytic dehydrogenation ofsec-alcohols withtert-butylhydroperoxide
Wang, Weilu,He, Yang,He, Junkai,Dang, Yanliu,Kankanmkapuge, Tharindu,Gao, Wenliang,Cong, Rihong,Suib, Steven L.,Yang, Tao
, p. 1365 - 1374 (2021/03/14)
Catalytic oxidation reaction using green oxidants plays an important role in modern chemical engineering; however, thein situgenerated active species and the related catalytic mechanism need to be understood in depth. For this purpose, Cr-substituted aluminoborate Cr-PKU-8 catalysts were synthesized and applied as recyclable heterogeneous catalysts for the oxidation of aliphatic and aromatic alcohols usingtert-butylhydroperoxide (TBHP). Both high efficiency and selectivity (>99%) were achieved during the dehydrogenation of varioussec-alcohols into acetone in H2O solvent medium. From the analyses using isotopic tracer, molecular probe and cyclic voltammetry strategies, the chromium ions were observed to undergo a Cr3+-Cr2+-Cr3+redox cycle. DFT calculations suggest thatt-BuOO* is more energetically favourable for hydrogen abstraction fromsec-alcohol thant-BuO*, and probably acts as the key active species. Accordingly, the reaction scheme was proposed to interpret the catalytic process based on the observed results.
