- Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
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The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
- Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
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p. 645 - 656
(2020/05/14)
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- Peptidylarginine deiminase inhibitor and application thereof
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The invention belongs to the technical field of medicine, and particularly relates to a peptidylarginine deiminase PAD4 inhibitor compound shown in a formula (I) or pharmaceutically acceptable salts,stereoisomers and tautomers thereof, as well as pharmaceutical compositions, pharmaceutical preparations and application thereof. X, Y, R1, R2, R3, R4, R5, R7, R8, R9, ring B and m are as defined in the specification. The compound has inhibitory effect on peptidylarginine deiminase PAD4, and can be used for treating various diseases, such as rheumatoid arthritis, vasculitis, systemic lupus erythematosus, ulcerative colitis, multiple sclerosis, cystic fibrosis, cancer, cutaneous lupus erythematosus, asthma and psoriasis.
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- Rhodium-Catalyzed Formylation of Aryl Halides with CO2 and H2
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The reductive formylation of aryl iodides/bromides to aryl aldehydes using CO2/H2 is presented for the first time. It was realized over a catalytic system composed of RhI3 or RhI3/Pd(dppp)Cl2 (dppp = 1,3-bis(diphenyphosphino)propane) and PPh3 in the presence of Ac2O/Et3N at 100 °C, affording aromatic aldehydes in good to excellent yields, together with good functional-group tolerance and broad substrate scope. The reaction proceeds through three cascade steps, involving HCOOH formation, CO release, and formylation of aryl halides.
- Liu, Zhenghui,Yang, Zhenzhen,Yu, Bo,Yu, Xiaoxiao,Zhang, Hongye,Zhao, Yanfei,Yang, Peng,Liu, Zhimin
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p. 5130 - 5134
(2018/09/13)
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- A 3 - furfural types of the product of preparation method (by machine translation)
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The invention discloses a 3 - furfural such product of preparation method, selecting palladium catalyst, heteropoly acid catalyst and Lewis acid catalyst is dissolved in a concentration of 1 mol/L solvent three-opening in the bottle, the water bath is heated to 40 - 90 °C; selecting the α, β - unsaturated carboxylic acid ester and fatty aldehyde phase mixing, the mixed solution is added to the flask in, then in 40 - 90 °C stirring under reflux reaction; to after the completion of the reaction, adding the extractant after separating distilled under reduced pressure to obtain 3 - furfuryl acid esters, a reducing agent is added to the reaction flask in 3 - furfural types of product. This invention adopts the α, β - unsaturated carboxylic acid esters, aliphatic aldehydes and heteropoly acid catalyst and the like, are commonly used chemical reagent, low cost, easy operation, can carry out a large number of production, small pollution to the environment, it is environment-friendly reaction; at the same time the invention the provided 3 - furfural types of product, it is a kind of has a wide application prospect of intermediate, its downstream product synthesis and application of, with broad application prospect. (by machine translation)
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Paragraph 0020; 0021
(2018/03/25)
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- Heterogeneous Sodium-Manganese Oxide Catalyzed Aerobic Oxidative Cleavage of 1,2-Diols
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The aerobic oxidative cleavage of 1,2-diols using a heterogeneous catalyst only based on earth-abundant metals manganese and sodium is reported for the first time. This reusable catalyst cleaves a variety of substrates into aldehydes or ketones with high selectivity. The reaction requires small catalytic loadings and is performed under mild conditions using ambient pressure O2 or air as the oxidant while producing water as the only by-product. Mechanistic investigations reveal a monodentate, two-electron oxidative fragmentation process involving a MnIV species. The eco-friendly, innocuous catalyst is compatible with a wide range of functional groups and conditions, making it highly competitive with classical reagents, such as periodic acid or lead tetraacetate, as a preferred method for activated 1,2-diols.
- Escande, Vincent,Lam, Chun Ho,Coish, Philip,Anastas, Paul T.
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supporting information
p. 9561 - 9565
(2017/08/01)
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- Aerobic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by N-Hydroxyphthalimide (NHPI) Combined with CoTPP-Zn2Al-LDH
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A catalytic system for the aerobic oxidation of alcohols by N-hydroxyphthalimide (NHPI) combined with cobalt porphyrin intercalated heterogeneous hybrid catalyst (CoTPP-Zn 2Al-LDH) has been developed. The results showed that this catalytic system can effectively catalyze the oxidation of alcohols to the corresponding carbonyl compounds. And the hybrid catalyst can be reused for five times with no appreciable reduction of activity. [Figure not available: see fulltext.]
- Zhou, Weiyou,Chen, Dongwei,Cui, Aijun,Qian, Junfeng,He, Mingyang,Chen, Qun
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p. 295 - 299
(2017/03/23)
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- A general and efficient zinc-catalyzed oxidation of benzyl alcohols to aldehydes and esters
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Go green: A general and efficient zinc-catalyzed oxidation of benzyl alcohols has been developed. In the presence of a zinc catalyst, various aldehydes and esters have been prepared in good to excellent yields under mild conditions (see scheme).
- Wu, Xiao-Feng
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experimental part
p. 8912 - 8915
(2012/09/22)
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- Palladium-catalyzed direct oxidation of alkenes with molecular oxygen: General and practical methods for the preparation of 1, 2-diols, aldehydes, and ketones
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(Figure Presented) 1, 2-Diols, aldehydes, and ketones are important intermediates in chemical synthesis, and alkenes are possible precursors for 1, 2-diols, aldehydes, and ketones. Herein, novel and environmentally benign methods for palladium-catalyzed dihydroxylation and oxidative cleavage of olefins with oxygen as sole oxidant are presented. The cleavage reactions were performed with acid as additive in aqueous solution, whereas 1, 2-diols were formed in the presence of base. A broad substrate scope has been demonstrated allowing monosubstituted aromatic and aliphatic terminal alkenes, 1, 2-disubstituted, and 1, 1-disubstituted olefins. The cleavage reactions of dioxo-PdII complexes implicate 1, 2-diol might act as a key intermediate of olefin cleavage.
- Wang, Azhong,Jiang, Huanfeng
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supporting information; experimental part
p. 2321 - 2326
(2010/07/04)
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- GAS PHASE REACTION PROCESS FOR POLYHYDRIC COMPOUNDS
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The present invention provides processes for the gas phase conversion of a polyhydric feedstock into an oxygen-containing product. The polyhydric feedstock comprises water and at least one polyhydric compound having from about four to about twelve carbon atoms and more than three hydroxyl groups. Also provided are processes for the separation of the oxygen-containing product from the reaction product mixture.
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Page/Page column 20-21
(2008/12/07)
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- Solvent applications of 2-methyltetrahydrofuran in organometallic and biphasic reactions
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2-Methyltetrahydrofuran (MeTHF) is a commercially available solvent that is produced from renewable resources. The properties of MeTHF place it between tetrahydrofuran (THF) and diethyl ether in solvent polarity and Lewis base strength. In many cases, MeTHF can replace THF in organometallic reactions. The formation and reaction of Grignard reagents in MeTHF and THF are similar. MeTHF can be used as a solvent for low-temperature lithiation, for lithium aluminum hydride reductions, for the Reformatsky reaction, and for metal-catalyzed coupling reactions. MeTHF is also a good substitute for dichloromethane in biphasic reactions.
- Aycock, David F.
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p. 156 - 159
(2012/12/26)
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- PROCESS FOR HETEROGENEOUSLY CATALYZED PARTIAL GAS PHASE OXIDATION OF PROPYLENE TO ACRYLIC ACID
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A process for heterogeneously catalyzed partial gas phase oxidation of propylene to acrylic acid, in which the starting reaction gas mixture comprises cyclopropane as an impurity and the acrylic acid, after conversion from the product gas mixture into the condensed phase, is removed with the aid of a crystallative removal.
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Page/Page column 20-22
(2008/06/13)
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- Mild and recyclable hypervalent iodine system for oxidation of alcohols
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A simple and mild system for oxidation of primary and secondary alcohols to corresponding aldehydes and ketones has been developed using 4,4′-bis (dichloroiodo) biphenyl in combination with tetraethylammonium bromide (TEAB) at room temperature. Facile recovery and recyclability of the oxidant is reported. Copyright Taylor & Francis Group, LLC.
- Telvekar, Vikas N.,Herlekar, Omkar P.
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p. 859 - 863
(2007/10/03)
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- CaS2O8: An efficient reagent for etherification of alcohols under microwave irradiation in solvent-free conditions
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A new facile and efficient one-pot method for the synthesis of ethers by the reaction of alcohols with calcium peroxodisulfate under microwave irradiation is described. Copyright Taylor & Francis Group, LLC.
- Badri, Rashid,Kiasat, Ali Reza,Nazari, Simin
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p. 589 - 593
(2007/10/03)
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- Process for removing methacrylic acid from liquid phase comprising acrylic acid as a main constituent and target product, and methacrylic acid as a secondary component
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A process for removing methacrylic acid from liquid phase P comprising acrylic acid as a main constituent and target product, and methacrylic acid as a secondary component in which the removal is effected by crystallization, the acrylic acid accumulating in the crystals formed and the methacrylic acid in the remaining mother liquor.
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Page/Page column 8-9
(2008/06/13)
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- Inhibitors of glycogen synthase kinase 3
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Novel pyridine and pyrimidine derivatives which selectively inhibit glycogen synthase kinase 3 are provided and methods of preparing these compounds are provided. These compounds are useful in treating certain conditions which may be mediated by glycogen synthase kinase 3.
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- Direct hydrogenation of carboxylic acids to corresponding aldehydes catalyzed by palladium complexes
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A variety of carboxylic acids can be directly hydrogenated into the corresponding aldehydes in high yields by using homogeneous catalysts such as [Pd(PPh3)4] or combination of Pd(OAc)2 with tertiary phosphines in the presence of an excess amount of 2,2-dimethylpropionic anhydride (pivalic anhydride). As a typical example, octanoic acid can be convened into octanal in 99% yield in 3 h at 80 °C under 3.0 MPa of H2 in acetone in the presence of pivalic anhydride and a catalyst system composed of Pd(OAc)2 + 5P(p-tol)3. Such hydrogenation is widely applicable to various aliphatic, aromatic, and heterocyclic carboxylic acids as well as to di- and tribasic carboxylic acids. The process allows the presence of other functional groups such as ketonic carbonyl, nitrile, and ester groups and even internal C=C bonds. Heterogeneous palladium catalyst such as palladium on carbon also showed some catalytic activities.
- Nagayama,Shimizu,Yamamoto
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p. 1803 - 1815
(2007/10/03)
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- Isoquinoline compound melanocortin receptor ligands and methods of using same
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The invention relates to melanocortin receptor ligands and methods of using the ligands to alter or regulate the activity of a melanocortin receptor. The invention further relates to tetrahydroisoquinoline aromatic amines that function as melanocortin receptor ligands and as agents for controlling cytokine-regulated physiologic processes and pathologies, and combinatorial libraries thereof.
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- Polymer pyrolysis and oxidation studies in a continuous feed and flow reactor: Cellulose and polystyrene
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A dual-zone, continuous feed tubular reactor is developed to assess the potential for formation of products from incomplete combustion in thermal oxidation of common polymers. Solid polymer (cellulose or polystyrene) is fed continuously into a volatilization oven where it fragments and vaporizes. The gas-phase polymer fragments flow directly into a second, main flow reactor to undergo further reaction. Temperatures in the main flow reactor are varied independently to observe conditions needed to convert the initial polymer fragments to CO2 and H2O. Combustion products are monitored at main reactor temperatures from 400 to 850 °C and at 2.0-s total residence time with four on-line GC/FIDs; polymer reaction products and intermediates are further identified by GC/MS analysis. Analysis of polymer decomposition fragments at 400 °C encompasses complex oxygenated and aromatic hydrocarbon species, which range from high-molecular-weight intermediates of ca. 300 amu, through intermediate mass ranges down to C1 and C2 hydrocarbons, CO, and CO2. Approximately 41 of these species are positively identified for cellulose and 52 for polystyrene. Products from thermal oxidation of cellulose and polystyrene are shown to achieve complete combustion to CO2 and H2O at a main reactor temperature of 850 °C under fuel-lean equivalence ratio and 2.0-s reaction time. A dual-zone, continuous feed tubular reactor is developed to assess the potential for formation of products from incomplete combustion in thermal oxidation of common polymers. Solid polymer (cellulose or polystyrene) is fed continuously into a volatilization oven where it fragments and vaporizes. The gas-phase polymer fragments flow directly into a second, main flow reactor to undergo further reaction. Temperatures in the main flow reactor are varied independently to observe conditions needed to convert the initial polymer fragments to CO2 and H2O. Combustion products are monitored at main reactor temperatures from 400 to 850°C and at 2.0-s total residence time with four on-line GC/FIDs; polymer reaction products and intermediates are further identified by GC/MS analysis. Analysis of polymer decomposition fragments at 400°C encompasses complex oxygenated and aromatic hydrocarbon species, which range from high-molecular-weight intermediates of ca. 300 amu, through intermediate mass ranges down to C1 and C2 hydrocarbons, CO, and CO2. Approximately 41 of these species are positively identified for cellulose and 52 for polystyrene. Products from thermal oxidation of cellulose and polystyrene are shown to achieve complete combustion to CO2 and H2O at a main reactor temperature of 850°C under fuel-lean equivalence ratio and 2.0-s reaction time.
- Park, Byung-Ik,Bozzelli, Joseph W.,Booty, Michael R.,Bernhard, Mary J.,Mesuere, Karel,Pettigrew, Charles A.,Shi, Ji-Chun,Simonich, Staci L.
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p. 2584 - 2592
(2007/10/03)
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- Mild and convenient oxidation of aromatic heterocyclic primary alcohols by 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium perchlorate
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Hydroxymethyl substituted aromatic heterocycles, including pyridines, furans, and thiophenes, are oxidized to the corresponding aldehydes in excellent yields by 4-acetylamino-2,2,6,6-tetramethylpiperidine-1- oxoammonium perchlorate (1) with minimal workup.
- Kernag, Casey A.,Bobbitt, James M.,McGrath, Dominic V.
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p. 1635 - 1636
(2007/10/03)
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- 1-cyclopropyl-4-pyridyl-quinolinones
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Compounds of formula STR1 wherein R1 is hydrogen, lower-alkyl, or trifluoromethyl; R2 is lower-alkyl, trifluoromethyl or CH2 Z where Z is hydroxy, chloro, lower-alkylamino or dilower-alkylamino; R3 and R4 are each individually hydrogen or fluoro; and Ar is phenyl, an aromatic 5- or 6-membered heterocycle or any of these substituted at one or more positions with lower-alkyl, fluoro, chloro, hydroxy, amino, lower-alkylamino, dilower-alkylamino, carboxy, sulfonamido, lower alkylsulfonamido, methylenedioxy, trifluoroacetamido, lower-alkanoylamino, or carbamoyl; and their pharmaceutically acceptable acid addition salts are useful as anticancer agents.
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- A Mild Oxidizing Reagent for Alcohols and 1,2-Diols: o-Iodoxybenzoic Acid (IBX) in DMSO
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o-Iodoxybenzoic acid (IBX) smoothly oxidizes primary and secondary alcohols to aldehydes and ketones, respectively. 1,2-Diols are converted to α-ketols or α-diketones without any oxidative cleavage of the glycol C-C bond.IBX oxidations are easily conducted in DMSO solution at room temperature, with yields ranging from good to quantitative.
- Frigerio, Marco,Santagostino, Marco
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p. 8019 - 8022
(2007/10/02)
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- OXIDATION CHEMISTRY OF A cis-2-(3-FURYLIDENE)ETHANOL
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Submission of the tri-n-butylstannylmethyl ether (9) of furylcarbinol (8) to Still rearrangement leads stereoselectively to 10 as the exclusive product.The cis-oriented nature of the hydroxyethyl and 3-furyl functional groups in 10 is cause for ready ring closure either to benzofuran (10) or lactone (13) depending upon conditions.
- Fristad, William E.,Paquette, Leo A.
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p. 2219 - 2224
(2007/10/02)
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- Chiral Multifunctional Isoprene Units by Ring-Contraction of Riboside Oxiranes
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Lithium bromide induced ring-contraction of benzyl 2,3- and 3,4-anhydro-β-D(and L)-ribopyranoside (1 and 4) in HMPA/toluene or tetramethylurea (TMU)/toluene gave (R)(and S)-2-(benzyloxy)-2,5-dihydrofufan-4-carboxaldehyde (2 and 5) together with a small amount of benzyl 4-bromo-4-deoxy-β-L(and D)-lyxopyranoside (3 and 6).The latter compound was formed with lithium bromide in 1,1,1-trichloroethane.Benzyl 2,3- and 3,4-anhydro-2-deuterio-β-L-ribopyranoside (4d and 8d) gave the deuterated aldehyde 5d, which carried a vinylic deuterium atom, wheraes benzyl 2,3-anhydro-4-deuterio-β-L-ribopyranoside (4d' ) gave the nondeuterated aldehyde 5.On the basis of these experiments, the mechanism of the ring-contraction as postulated.
- Sundin, Anders,Frejd, Torbjoern,Magnusson, Goeran
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p. 3927 - 3930
(2007/10/02)
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- AN IMPROVED SYNTHESIS OF 2-METHYL-4-(2'-CARBOXYETHYL)PYRROLE. POTENTIAL INHIBITORS OF PORPHOBILINOGEN DEAMINASE
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Improved syntheses of 2-methyl-4-(2'-carboxyethyl)pyrrole (10) (49percent overall yield) and of several O- and S-containing β-(5-ring heterocyclic)-substituted propionic acid are described.Some of these compounds have been found to be inhibitors of porphobilinogen deaminase.
- Wilen, Samuel H.,Shen, DeKang,Licata, Joseph M.,Baldwin, Enoch,Russell, Charlotte S.
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p. 1747 - 1757
(2007/10/02)
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- Total synthesis of thienamycin analogs - III. Synthesis of 2-aryl and 2-heteroaryl analogs of theinamycin
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The total syntheses of 2-aryl and 2-heteroaryl carbapen-2-em-3-carboxylic acids with and without a 6-hydroxyethyl side chain, using Wittig cyclization for formation of the bicyclic ring system is described. Antibacterial activity of the compounds synthesized is discussed.
- Cama,Wildonger,Guthikonda,et al.
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p. 2531 - 2549
(2007/10/02)
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- Furopyridines. I. Synthesis of Furopyridine
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The parent framework of furopyridine has been synthesized. 3-Furoic acid chloride (2) was reduced with bis(triphenylphosphine) copper(I) tetrahydroborate to afford 3-furaldehyde (3) which was condensed with malonic acid to give β-(3-furyl)acrylic acid (4).The acrylic acid 4 was converted to the acid azide (5), which in turn was cyclized to give furopyridin-7(6H)-one (6) by heating at 180 deg in diphenylmethane.The pyridone 6 was chlorinated with phosphorus oxychloride, followed by reduction with zinc and acetic acid to give furopyridine (8).
- Shiotani, Shunsaku,Morita, Hiroyuki
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p. 1207 - 1209
(2007/10/02)
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- Hypoglycemic 5-substituted oxazolidine-2,4-diones
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Hypoglycemic 5-furyl and 5-thienyl derivatives of oxazolidine-2,4-dione and the pharmaceutically-acceptable salts thereof; certain 3-acylated derivatives thereof; and intermediates useful in the preparation of said compounds.
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- STRUCTURE OF AN ANTITUMOR ANTIBIOTIC, REDUCTIOMYCIN
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The structure of an antitumor antibiotic isolated from a variant of Streptomyces orientalis was established as (1) by chemical and spectral evidence.The antibiotic was found to be identcal with reductiomycin, and therefore the structure (X) of reductiomycin previously reported must be revised.
- Shizuri, Yoshikazu,Ojika, Makoto,Yamada, Kiyoyuki
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p. 4291 - 4294
(2007/10/02)
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- Selenium--Stabilized Anions. Preparation of α,β-Unsaturated Carbonyl Compounds Using Propargyl Selenides. Synthesis of (+/-)-7-Hydroxymyoporone
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The reaction of alkyl halides, carbonyl compounds, and trimethylsilyl chloride with the mono- and dianion (1) prepared by deprotonation of phenyl propargyl selenide with lithium diisopropylamide gives 1- or 3-monosubstituted or 1,3-disubstituted propargyl selenides (3a).Oxidation to selenoxides (3b) results in rearrangement to 2-(phenylseleno)-1,3-disubstituted propenones.The rate of rearrangement of propargyl selenoxides increases dramatically when the phenyl group is replaced by a 2-nitrophenyl group, and an intermediate allenyl selenate ester (7c) can be observed by low-temperature NMR.By appropriate modification of oxidation conditions, modest yields of 2-iodopropenes (e.g., 10) or the selenium-free enones or enals can be obtained.A synthesis of (+/-)-7-hydroxymyoporone (15) and its epimer has been carried out by using the dianion 1 to assemble the carbon skeleton.The preparation of α-lithioallenyl phenyl selenide (26) has been accomplished, and its reaction with electrophiles has been studied.
- Reich, Hans J.,Shah, Shrenik K.,Gold Paul M.,Olson Richard E.
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p. 3112 - 3120
(2007/10/02)
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