- Ullman Ether Synthesis in DMI. Preparation of m-Phenoxybenzyl Alcohol
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The condensation of m-hydroxybenzyl alcohol with chlorobenzene was examined in several different solvents, and an effective route to m-phenoxybenzyl alcohol has been developed by using 1,3-dimethyl-2-imidazolidinone (DMI) as a solvent.
- Oi, Ryu,Shimakawa, Chitoshi,Takenaka, Shinji
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Read Online
- KF-Al2O3 mediated cross-Cannizzaro reaction under microwave irradiation
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Aromatic aldehydes are selectively converted to the corresponding alcohols in high yields by cross-Cannizzaro reaction using KF-Al2O3 under microwave irradiation in solvent-free condition.
- Subba Reddy,Srinivas,Yadav,Ramalingam
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Read Online
- Improving metabolic stability with deuterium: The discovery of HWL-066, a potent and long-acting free fatty acid receptor 1 agonists
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The free fatty acid receptor 1 (FFA1) is a potential target due to its function in enhancing of glucose-stimulated insulin secretion. The FFA1 agonist GW9508 has great potential for the treatment of type 2 diabetes mellitus, but it has been suffering from high plasma clearance probably because the phenylpropanoic acid is vulnerable to β-oxidation. To identify orally available analog without influence on the unique pharmacological mechanism of GW9508, we tried to interdict the metabolically labile group by incorporating two deuterium atoms at the α-position of phenylpropionic acid affording compound 4 (HWL-066). As expected, HWL-066 revealed a lower clearance (CL?=?0.23?L?1?hr?1?kg?1), higher maximum concentration (Cmax?=?5907.47?μg/L), and longer half-life (T1/2?=?3.50?hr), resulting in a 2.8-fold higher exposure than GW9508. Moreover, the glucose-lowering effect of HWL-066 was far better than that of GW9508 and comparable with TAK-875. Different from glibenclamide, no side-effect of hypoglycemia was observed in mice after oral administrating HWL-066 (80?mg/kg).
- Liu, Chunxia,Li, Zheng,Shi, Wei,Li, Huilan,Wang, Nasi,Dai, Yuxuan,Liao, Chen,Huang, Wenlong,Qian, Hai
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Read Online
- Thermal decomposition and isomerization of cis-permethrin and β-cypermethrin in the solid phase
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The stability to heat of cis-permethrin and β-cypermethrin in the solid phase was studied and the decomposition products identified. Samples heated at 210°C in an oven in the dark showed that, in the absence of potassium chlorate (the salt present in smoke-generating formulations of these pyrethroids), cis-permethrin was not isomerized, although in the presence of that salt, decomposition was greater and thermal isomerization occured. Other salts of the type KXO3 or NaXO3, with X being halogen or nitrogen, also led to a considerable thermal isomerization. Heating the insecticides in solution in the presence of potassium chlorate did not produce isomerization in any of the solvents assayed. Salt-catalysed thermal cis-trans isomerization was also found for other pyrethroids derived from permethrinic or deltamethrinic acid but not for those derived from chrysanthemic acid. The main thermal degradation processes of cis-permethrin and β-cypermethrin decomposition when potassium chlorate was present were cyclopropane isomerization, ester cleavage and subsequent oxidation of the resulting products. Permethrinic acid, 3-phenoxybenzyl chloride, alcohol, aldehyde and acid were identified in both cases, as well as 3-phenoxybenzyl cyanide from β-cypermethrin. A similar decomposition pattern occurred after combustion of pyrethroid fumigant formulations.
- Audino, Paola Gonzalez,Licastro, Susana A.,Zerba, Eduardo
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Read Online
- Phenylpropiolic acid small molecular organic compounds and synthetic method and application thereof
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The invention relate to a category of novel phenylpropiolic acid small molecular organic compounds as shown in a structural formula (I) or stereisomers, crystals, hydrates or pharmaceutically acceptable salt and an application of the phenylpropiolic acid small molecular organic compounds or stereisomers, crystals, hydrates or pharmaceutically acceptable salt and pharmaceutical compositions comprising the compounds in preparing a GPR40 agonist and drugs for promoting insulin release, treating and/or preventing diabetes or complications, treating diabetes inducing poor therapeutic effect inducedby acquired drug-resistance and complications and the like. The invention also provides a preparation method of the phenylpropiolic acid small molecular organic compounds as shown in the structural formula (I). The phenylpropiolic acid small molecular organic compounds have good anti-diabetes effect and the risk of inducing hypoglycemia is lower than that of conventional drugs.
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Paragraph 0070; 0071; 0072
(2019/04/13)
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- IMPROVED METHOD FOR THE SYNTHESIS OF PERMETHRIN
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The present invention describes an improved method for the synthesis of substantially pure Permethrin (1) having purity greater than 99.5% by Gas Chromatography (GC). The invention also relates to a purification process of Permethrin by recrystallization from methanol-water mixture.
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Page/Page column 7; 8
(2018/03/25)
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- Methanol as hydrogen source: Transfer hydrogenation of aromatic aldehydes with a rhodacycle
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A cyclometalated rhodium complex has been shown to perform highly selective and efficient reduction of aldehydes, deriving the hydrogen from methanol. With methanol as both the solvent and hydrogen donor under mild conditions and an open atmosphere, a wide range of aromatic aldehydes were reduced to the corresponding alcohols, without affecting other functional groups.
- Aboo, Ahmed H.,Bennett, Elliot L.,Deeprose, Mark,Robertson, Craig M.,Iggo, Jonathan A.,Xiao, Jianliang
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supporting information
p. 11805 - 11808
(2018/11/10)
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- Novel deuterated phenylpropionic acid derivative, preparation method thereof, and use of derivative as medicine
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The invention relates to a novel deuterated phenylpropionic acid derivative represented by general formula (I), a preparation method thereof, and a use of a medicinal composition containing the derivative as a medicine for treating diabetes and metabolic syndrome. The deuterated phenylpropionic acid derivative has excellent in vivo blood sugar lowering activity, and can be used for preparing medicines for preventing or treating diabetes.
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- Copper-Catalyzed Diaryl Ether Formation from (Hetero)aryl Halides at Low Catalytic Loadings
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Diaryl formation is achieved by coupling phenols and (hetero)aryl halides under the catalysis of CuI/N,N′-bis(2-phenylphenyl) oxalamide (BPPO) or CuI/N-(2-phenylphenyl)-N′-benzyl oxalamide (PPBO) at 90 °C using DMF or MeCN as the solvent. Only 0.2-2 mol % CuI and ligand are required for complete conversion, which represents the lowest catalytic loadings for a general Cu/ligand-catalyzed diaryl ether formation.
- Zhai, Yuntong,Chen, Xiaofei,Zhou, Wei,Fan, Mengyang,Lai, Yisheng,Ma, Dawei
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p. 4964 - 4969
(2017/05/12)
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- Conformational Constraint of the Glycerol Moiety of Lysophosphatidylserine Affords Compounds with Receptor Subtype Selectivity
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Lysophosphatidylserine (LysoPS) is an endogenous lipid mediator that specifically activates membrane proteins of the P2Y and its related families of G protein-coupled receptors (GPCR), GPR34 (LPS1), P2Y10 (LPS2), and GPR174 (LPS3). Here, in order to increase potency and receptor selectivity, we designed and synthesized LysoPS analogues containing the conformational constraints of the glycerol moiety. These reduced structural flexibility by fixation of the glycerol framework of LysoPS using a 2-hydroxymethyl-3-hydroxytetrahydropyran skeleton, and related structures identified compounds which exhibited high potency and selectivity for activation of GPR34 or P2Y10. Morphing of the structural shape of the 2-hydroxymethyl-3-hydroxytetrahydropyran skeleton into a planar benzene ring enhanced the P2Y10 activation potentcy rather than the GPR34 activation.
- Jung, Sejin,Inoue, Asuka,Nakamura, Sho,Kishi, Takayuki,Uwamizu, Akiharu,Sayama, Misa,Ikubo, Masaya,Otani, Yuko,Kano, Kuniyuki,Makide, Kumiko,Aoki, Junken,Ohwada, Tomohiko
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supporting information
p. 3750 - 3776
(2016/05/19)
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- Indium(III) Isopropoxide as a Hydrogen Transfer Catalyst for Conversion of Benzylic Alcohols into Aldehydes or Ketones via Oppenauer Oxidation
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Indium(III) isopropoxide [In(Oi-Pr)3] was applicable as an Oppenauer oxidation catalyst, and the conversion of primary or secondary alcohols into the corresponding aldehydes or ketones was promoted at room temperature using pivalaldehyde as an oxidant.
- Ogiwara, Yohei,Ono, Yuji,Sakai, Norio
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p. 4143 - 4148
(2016/11/26)
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- CuI/oxalamide catalyzed couplings of (hetero)aryl chlorides and phenols for diaryl ether formation
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Couplings between (hetero)aryl chlorides and phenols can be effectively promoted by CuI in combination with an N-aryl-N′-alkyl-substituted oxalamide ligand to proceed smoothly at 120 °C. For this process, N-aryl-N′-alkyl-substituted oxalamides are more effective ligands than bis(N-aryl)-substituted oxalamides. A wide range of electron-rich and electron-poor aryl and heteroaryl chlorides gave the corresponding coupling products in good yields. Satisfactory conversions were achieved with electron-rich phenols as well as a limited range of electron-poor phenols. Catalyst and ligand loadings as low as 1.5 mol % are sufficient for the scaled-up variants of some of these reactions. Aryl and alkyl: N-Aryl-N′-alkyl-substituted oxalamide ligands promote the CuI catalyzed coupling of (hetero)aryl chlorides and phenols at 120 °C more effectively than bis(N-aryl)-substituted oxalamides. A wide range of electron-rich and electron-poor aryl and heteroaryl chlorides were converted into the corresponding coupling products in good yields.
- Fan, Mengyang,Zhou, Wei,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 6211 - 6215
(2016/05/24)
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- HETEROCYCLIC COMPOUNDS AS NAV CHANNEL INHIBITORS AND USES THEREOF
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The present invention relates to heterocyclic compounds of formula (I) wherein: Z1 is C(R)(R), C(O), C(S), or C(NR); 2 Z is C(R)(R), 0, S, SO, S02, or NR; X is -O-, -S-, -S02-, -SO-, -C(O)-, -C02-, -C(O)N(R)-, -NRC(O)-, -NRC(O) N(R)-, -NRSO2-, or -N(R)-; or X is absent; A is an optionally substituted C1_6 aliphatic, C5-10 aryl, 3-8 membered saturated or partially unsaturated carbocyclic ring, 3-7 membered heterocylic ring, or a 5-6 membered heteroaryl ring; Y is -CH2-, -O-, -S-, -S02-, -SO-, -C(O)-, -C02-, -C(O)N(R)-, -NRC(O)-, - NRC(O)N(R)-, -NRS02-, or -N(R)-; B is an optionally substituted C5-10 aryl or 5-6 membered heteroaryl ring; m is 0, 1, 2, or 3; n is 0, 1, 2, or 3; q is 0, 1, 2, or 3; and r is 1 or 2; and pharmaceutically acceptable compositions thereof, useful as Navl.6 inhibitors.
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Paragraph 00209
(2015/09/28)
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- Highly chemoselective hydrogenation of active benzaldehydes to benzyl alcohols catalyzed by bimetallic nanoparticles
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By using novel Pd/Ni bimetallic nanoparticles as a catalyst, the active benzaldehydes were hydrogenated to the corresponding benzyl alcohols as unique products in practical quantitative yields. The undesired catalytic hydrogenolysis of the benzyl alcohol was inhibited completely. By using this hydrogenation as a key step, the total synthesis of the natural product gastrodin was achieved with less total steps and a higher total yield.
- Liu, Chulong,Bao, Hailin,Wang, Dingsheng,Wang, Xinyan,Li, Yadong,Hu, Yuefei
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p. 6460 - 6462
(2015/11/16)
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- Chemoselective and ligand-free synthesis of diaryl ethers in aqueous medium using recyclable alumina-supported nickel nanoparticles
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An economical and eco-compatible ligand-free protocol for the synthesis of diaryl ethers has been developed using easily accessible alumina-supported nickel nanoparticles as a stable recyclable heterogeneous catalyst in aqueous medium along with a surfactant (SDS) and a mild base (K2CO3). Various sensitive functional groups like allyl, alkoxycarbonyl, formyl, oxo, chloro, bromo, amine and nitro were tolerated in the aforesaid method. Excellent chemoselectivity was demonstrated through competition experiments.
- Ghatak, Avishek,Khan, Sagar,Roy, Rimi,Bhar, Sanjay
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supporting information
p. 7082 - 7088
(2015/02/02)
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- Characterization of a novel thermophilic pyrethroid-hydrolyzing carboxylesterase from Sulfolobus tokodaii into a new family
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A novel gene ST2026 encoding a putative carboxylesterase from the thermophilic crenarchaeota Sulfolobus tokodaii (named EstSt7) was cloned and functionally overexpressed in Escherichia coli. The recombinant enzyme was purified to homogeneity after heat treatment, Ni-NTA affinity and Superdex-200 gel filtration chromatography. EstSt7 showed maximum activity at 80 C over 30 min and had a half-life of 180 min at 90 C. Its enzymatic activity was stable in the pH range of 8.0-10.0 with an optimum at 9.0. The enzyme exhibited significant esterase activity toward various p-nitrophenyl esters and the most preferable substrate was p-nitrophenyl butyrate (kcat/Km of 246.3 s-1 mM-1). In addition, EstSt7 showed high activity and stability against organic solvents (20% and 50% v/v) and detergents (1% and 5% v/v). Furthermore, EstSt7 could efficiently hydrolyze a wide range of synthetic pyrethroids including fenpropathrin, permethrin, cypermethrin, cyhalothrin, deltamethrin and bifenthrin, which makes it a potential candidate for the detoxification of pyrethroids for the purpose of biodegradation. Sequence alignment, phylogenetic analysis and comparison of the conserved motif reveal that this novel carboxylesterase EstSt7 should be grouped into a new bacterial lipase and esterase family.
- Wei, Tao,Feng, Shengxue,Shen, Yulong,He, Peixin,Ma, Geli,Yu, Xuan,Zhang, Fei,Mao, Duobin
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p. 225 - 232
(2013/10/21)
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- A novel oxidative transformation of alcohols to nitriles: An efficient utility of azides as a nitrogen source
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An efficient methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been developed. This methodology employs DDQ as an oxidant and TMSN3 as a source of nitrogen in the presence of a catalytic amount of Cu(ClO4)2·6H 2O.
- Rokade, Balaji V.,Malekar, Sanjeev K.,Prabhu, Kandikere Ramaiah
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supporting information; body text
p. 5506 - 5508
(2012/07/03)
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- Synthesis, biological evaluation, and molecular modeling investigation of chiral 2-(4-chloro-phenoxy)-3-phenyl-propanoic acid derivatives with PPARα and PPARγ agonist activity
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PPARs are ligand-activated transcription factors that govern lipid and glucose homeostasis and play a central role in cardiovascular disease, obesity, and diabetes. Herein, we present screening results for a series of chiral 2-(4-chloro-phenoxy)-3-phenyl-propanoic acid derivatives, some of which are potent PPARγ agonists as well as PPARα agonists. To investigate the binding modes of the most interesting derivatives into the PPARα and PPARγ binding clefts and evaluate their agonist activity, docking experiments, molecular dynamics simulations, and MM-PBSA analysis were performed.
- Fracchiolla, Giuseppe,Lavecchia, Antonio,Laghezza, Antonio,Piemontese, Luca,Trisolini, Raffaella,Carbonara, Giuseppe,Tortorella, Paolo,Novellino, Ettore,Loiodice, Fulvio
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experimental part
p. 9498 - 9510
(2009/04/05)
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- High-throughput synthesis and analysis of acylated cyanohydrins
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The yields and optical purities of products obtained from chiral Lewis acid/Lewis base-catalysed additions of ct-ketonitriles to prochiral aldehydes could be accurately determined by an enzymatic method. The amount of remaining aldehyde was determined after its reduction to an alcohol, whilst the two product enantiomers were analysed after subsequent hydrolysis first by the (S)-selective Candida antarctica lipase B and then by the unselective pig liver esterase. The method could be used for analysis of products obtained from a number of aromatic aldehydes and aliphatic ketonitriles. Microreactor technology was successfully combined with high-throughput analysis for efficient catalyst optimization.
- Hamberg, Anders,Lundgren, Stina,Wingstrand, Erica,Moberg, Christina,Hult, Karl
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p. 4334 - 4341
(2008/02/08)
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- Molecular cloning, purification, and biochemical characterization of a novel pyrethroid-hydrolyzing esterase from Klebsiella sp. strain ZD112
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The gene encoding pyrethroid-hydrolyzing esterase (EstP) from Klebsiella sp. strain ZD112 was cloned into Escherichia coli and sequenced. A sequence analysis of the DNA responsible for the esfP gene revealed an open reading frame of 1914 bp encoding for a protein of 637 amino acid residues. No similarities were found by a database homology search using the nucleotide and deduced amino acid sequences of the esterases and lipases. EstP was heterologously expressed in E. coli and purified. The molecular mass of the native enzyme was approximately 73 kDa as determined by gel filtration. The results of sodium dodecyl sulfate - polyacrylamide gel electrophoresis and the deduced amino acid sequence of EstP indicated molecular masses of 73 and 73.5 kDa, respectively, suggesting that EstP is a monomer. The purified EstP not only degraded many pyrethroid pesticides and the organophosphorus insecticide malathion, but also hydrolyzed ρ-nitrophenyl esters of various fatty acids, indicating that EstP is an esterase with broad substrates. The Km for trans- and cis-permethrin and kcat/Km values indicate that EstP hydrolyzes both these substrates with higher efficiency than the carboxylesterases from resistant insects and mammals. The catalytic activity of EstP was strongly inhibited by Hg2+, Ag+, and ρ-chloromercuribenzoate, whereas a less pronounced effect (3-8% inhibition) was observed in the presence of divalent cations, the chelating agent EDTA, and phenanthroline.
- Wu, Pei C.,Liu, Yu H.,Wang, Zhuo Y.,Zhang, Xiao Y.,Li, He,Liang, Wei Q.,Luo, Na,Hu, Ji M.,Lu, Jia Q.,Luan, Tian G.,Cao, Li X.
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p. 836 - 842
(2007/10/03)
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- Purification and characterization of a novel pyrethroid hydrolase from Aspergillus niger ZD11
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The pyrethroid pesticides residues on foods and environmental contamination are a public safety concern. Pretreatment with pyrethroid hydrolase has the potential to alleviate the conditions. For this purpose, a fungus capable of using pyrethroid pesticides as a sole carbon source was isolated from the soil and characterized as Aspergillus niger ZD11. A novel pyrethroid hydrolase from cell extract was purified 41.5-fold to apparent homogeneity with 12.6% overall recovery. It is a monomeric structure with a molecular mass of 56 kDa, a pl of 5.4, and the enzyme activity was optimal at 45°C and pH 6.5. The activities were strongly inhibited by Hg2+, Ag+, and p-chloromercuribenzoate, whereas less pronounced effects (5-10% inhibition) were observed in the presence of the remaining divalent cations, the chelating agent EDTA and phenanthroline. The purified enzyme hydrolyzed various insecticides with similar carboxylester. trans-Permethrin is the preferred substrate.
- Liang, Wei Q.,Wang, Zhuo Y.,Li, He,Wu, Pei C.,Hu, Ji M.,Luo, Na,Cao, Li X.,Liu, Yu H.
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p. 7415 - 7420
(2007/10/03)
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- Uncatalyzed Meerwein-Ponndorf-Oppenauer-Verley Reduction of Aldehydes and Ketones under Supercritical Conditions
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When a solution of a carbonyl compound in alcohol (primary or secondary) is heated to ca. 300 °C, a disproportionation reaction, in which a carbonyl compound is reduced to the corresponding alcohol and the alcohol is oxidized to the corresponding ketone, takes place. This uncatalyzed variation of the Meerwein-Ponndorf-Oppenauer-Verley reaction gives, in certain cases, e.g., reduction of acetophenone or benzaldehyde by i-PrOH, almost quantitative yields. Yields are higher with secondary alcohols such as i-PrOH than with a primary alcohol such as EtOH. The reactions were also performed in a flow system by passing at a slow rate the same solutions through a glass or a metal coil heated to elevated temperatures. Ab initio calculations performed at the B3LYP/6-31G* level show that thermodynamically i-PrOH is a more potent reducing agent than EtOH by ca. 4 kcal/mol. The computations also show that in cases of aromatic carbonyl compounds, part of the deriving force is obtained from the entropy change of the reaction. The major contributor to the high yield, however, is the excess alcohol used, which shifts the equilibrium to the right. Calculated entropy of activation as well as isotopic H/D labeling suggest a cyclic transition state.
- Sominsky, Lena,Rozental, Esther,Gottlieb, Hugo,Gedanken, Aharon,Hoz, Shmaryahu
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p. 1492 - 1496
(2007/10/03)
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- CuCl2.2H2O MeOH. A new reagent system for the deprotection of tetrahydropyranyl ethers
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Cupric chloride dihydrate in methanol cleave the tetrahydropyranyl ethers to the corresponding alcohols in excellent yields under mild conditions.
- Davis, K. Joju,Bhalerao,Vittal Rao
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p. 2301 - 2308
(2007/10/03)
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- Physicochemical factors affecting the uptake by roots and translocation to shoots of amine bases in Barley
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The uptake by barley roots from nutrient solution and subsequent transport to shoots of two series of amine bases were measured over 6 to 72 h. The compounds were chosen to span systematically ranges of lipophilicity (assessed using 1-octanol/water partition coefficients, K(ow)) and pKa that would include commercial pesticide amines. In a series of six substituted phenethylamines, strong bases with pKa ~ 9.5, all the compounds were strongly taken up by roots from solutions of pH 8.0; uptake declined substantially as the pH was lowered to 5.0, especially for the compounds of intermediate lipophilicity (log K(ow)8 2 to 3). This uptake could be ascribed to three processes: (i) accumulation of the cation inside the root cells due to the negative charge on the plasmalemma, as given by the Nernst equation and important only for the polar compounds which have low permeation rates through membranes; (ii) accumulation into the vacuole by ion-trapping, which was the dominant process at high pH for all compounds and at all pH values for the compounds of intermediate lipophilicity; (iii) partitioning on to the root solids, substantial only for the most lipophilic compounds. Translocation to shoots was proportional to uptake by roots, this ratio being independent of external pH for each compound and being optimal for the compounds of intermediate lipophilicity. Such proportionality was also observed in a series of three weaker bases of intermediate lipophilicity, in which compounds of pKa 7.4 to 8.0 were also well taken up and translocated whereas the very weak base 4-ethylaniline (pKa 5-03) was much less so. Tests with quaternised pyridines confirmed that organic cations move only slowly through membranes. The observed behaviour of the amines could be modelled reasonably well assuming that transport within the plant was dominated by movement across membranes of the non-ionised species, and this appeared to be true even for the most lipophilic phenethylamine (log K(ow) 4.67) studied, though its long-distance movement would be as the protonated species.
- Inoue,Chamberlain,Bromilow
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- Correlation Analysis of Reactivity in the Oxidation of Substituted Benzyl Alcohols by Pyridinium Hydrobromide Perbromide
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Oxidation of monosubstituted benzyl alcohols by pyridinium hydrobromide perbromide (PHPB) leads to the formation of the corresponding benzaldehydes.The reaction is first order with respect to PHPB.Michaelis-Menten-type kinetics were observed with respect to he alcohol.The oxidation of α,α-dideuteriobenzyl alcohol indicated the presence of a substantial kinetic isotope effect.The rates of oxidation of meta- and para-substituted benzyl alcohols were correlated in terms of Taft's and Swain's dual substituent-parameter equations.The rates of the meta compounds correlated best with Taft's ?1 and ?0R values whereas the para-compounds showed an excellent correlation with Taft's ?1 and ?R + constants.The rates of the otho-substituted alcohols showed very good correlation with Charton's triparametric equation.The rate increased with an increase in the polarity of the solvent.A mechanism involving a rapid reversible formation of an intermediate complex and its subsequent decomposition in the rate-determining step has been proposed.
- Suri, Deepa,Banerji, Kalyan K.,Kothari, Seema
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p. 1734 - 1758
(2007/10/03)
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- Process for producing m-phenoxybenzyl alcohol
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A process for producing m-phenoxybenzyl alcohol by reacting chlorobenzene with m-hydroxybenzyl alcohol in the presence of a copper catalyst and a base, the process being characterized by using an alkylene glycol as a reaction solvent.
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- TWO PHASE REDUCTION OF AROMATIC ALDEHYDES BY MEANS OF SODIUM SULFIDE: ROLE OF POLYETHYLENE GLYCOLS
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Rate and selectivity of the reduction of benzaldehydes with aqueous sodium sulfide in a two phase system, could be improved by using 10 to 30 percent (W/V) of polyethylene glycols based on aqueous phase.
- Satagopan, V.,Chandalia, Sampatraj B.
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p. 1217 - 1224
(2007/10/02)
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- New arthropodicides
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Compounds with arthropodicidal activity having the general formula (I); STR1 wherein R1 is a halo group; or a lower alkyl, lower alkoxy or lower alkylthio group, in each of which the alkyl group may be substituted with one or more halo groups; R2 is hydrogen or a halo or methyl group; or R1 and R2 together form a methylenedioxy, or a difluoro-methylenedioxy group or, R1 and R2 together with the carbon atoms to which they are attached, form an aromatic ring; R3 is hydrogen, CN, or C≡CH; Y is --CH-- or --N--; Z is H or F; and X1, X2, X3, and X4 are the same or different and each is hydrogen or a fluoro, bromo or chloro group; with the proviso that Y is --N-- when Z is H.
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- The Selective Photocatalytic Oxidation of m-Phenoxytoluene on Titanium Dioxide Particles Supported in Nafion Membranes
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The selective photocatalytic oxidation of m-phenoxytoluene to m-phenoxybenzaldehyde on titanium dioxide (TiO2) particles incorporated in Nafion membranes has been investigated.No more than 0.1percent of by-products was detected after 24h irradation, and the catalytic nature of the reaction is demonstrated with a turnover in excess of 100.In addition, a yield of at least 28percent is achieved.Both the emission characteristics and catalytic activity of TiO2 are regenerated by washing the membrane in butanol.
- Lund, Elizabeth A.,Blatt, Edward,Furlong, D. Neil,Mau, Albert W. H.,Sasse, Wolfgang H. F.
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p. 1367 - 1373
(2007/10/02)
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- Photooxidation of m-Phenoxytoluene at Colloidal Titanium Dioxide/Non-Aqueous Solution Interfaces
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The selective photooxidation of m-phenoxytoluene to m-phenoxybenzaldehyde has been investigated in the system m-phenoxytoluene/O2/titanium dioxide/non-aqueous solvent/light.In acetonitrile the conversion was found to be c. 20percent with starting concentrations of m-phenoxytoluene in the range o.05-0.5 moldm-3.Adsorption of m-phenoxytoluene, m-phenoxybenzaldehyde or the intermediate product m-phenoxybenzyl alcohol from acetonitrile on titanium dioxide was not detectable by an equilibration/centrifugation/supernatant analysis technique.Photoemision and photoexcitation measurements, however, showed that m-phenoxytoluene and m-phenoxybenzyl alcohol, but not m-phenoxybenzaldehyde, formed charge-transfer complexes with titanium dioxide surfaces.The selectivity of the photooxidation is explained in terms of pathways involving these charge-transfer complexes.
- Blatt, Edward,Furlong, D. Neil,Mau, Albert W. -H.,Sasse, Wolfgang H. F.,Wells, Darrell
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p. 1351 - 1366
(2007/10/02)
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- Process for the preparation of diphenyl ether derivatives
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The invention relates to a process for the preparation of compounds of formula (I) STR1 wherein R1 stands for hydrogen or the group COR2, wherein R2 stands for a straight or branched chained alkyl having 1 to 8 carbon atoms optionally substituted with phenyl, naphthyl, tetrahydronaphthyl or m-phenoxy-benzyl, cycloalkyl having 3 to 6 carbon atoms optionally substituted with one or more straight or branched chained alkyl or alkenyl having 1 to 6 carbon atoms, phenyl or naphthyl. The compounds of formula (I) are prepared according to the invention by (a) reacting esters of formula (II) STR2 wherein X stands for chlorine or bromine and R2 has the same meanings as defined above with a phenol alkali metal salt and (b) if desired converting the diphenyl ethers so obtained to a specific compound of formula (I), m-phenoxybenzyl alcohol by the hydrolysis of the ester group.
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- Process for production of m-phenoxybenzyl alcohol
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A process for producing m-phenoxybenzyl alcohol which comprises reacting chlorobenzene with m-hydroxybenzyl alcohol in the presence of a copper compound as a catalyst and a base, characterized in that chlorobenzene is added to a polar solvent having a higher boiling point than chlorobenzene, the amount of chlorobenzene being 0.05 to 4.0 times the weight of the polar solvent; at least one compound selected from alkali hydroxides, alkali carbonates and alkali bicarbonates is used as the base in an amount of 1.0 to 2.0 gram-equivalents per mole of m-hydroxybenzyl alcohol; and the reaction is carried out at a temperature of 140° to 200° C. while removing the generated water as an azeotrope with chlorobenzene.
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- Pyrimidine substituted-2,2-dimethylcyclopropane carboxylates useful for combating insect and acarine pests at a locus
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A compound of formula: STR1 wherein R2 represents an α-branched alkyl group containing from 3 to 6 carbon atoms, and R represents either (a) hydroxy, halo or alkoxy of up to six carbon atoms, or (b) the group --OR1 where R1 is the residue of an alcohol of formula R1 OH which forms an insecticidal ester with chrysanthemic acid, permethrin acid or cyhalothrin acid. The compounds have insecticidal and acaricidal properties.
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- INTENSIFICATION OF CROSS-CANNIZZARO REACTION IN TWO-PHASE SYSTEM: m-PHENOXYBENZALDEHYDE AND m-BROMOBENZALDEHYDE WITH FORMALDEHYDE
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The cross-Cannizzaro reaction of m-phenoxybenzaldehyde and m-bromobenzaldehyde with aqueous formaldehyde in a two-phase system can be intensified and made more selective by using hydrotropes; cationic surfactants do not improve selectivity.
- Pramodchandra, V. Sane,Sharma, Man Mohan
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p. 1331 - 1338
(2007/10/02)
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- Pentafluorobenzyl esters
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The (+), (-) and (±) forms of the compounds of the general formula (I) STR1 characterized in that R1 is a halo group; or a lower alkyl, lower alkoxy or lower alkylthio group, each of which may be substituted with one or more halo groups; R2 is hydrogen or a methyl group; or R1 and R2 together form a methylenedioxy, or a difluoromethylenedioxy group or, with the carbon atoms to which they are attached, an aromatic or heteroaromatic ring; and A is one of the groups X or Y STR2 wherein X1 and X2 are the same or different and each is hydrogen or a fluoro, chloro, bromo or methyl group, with the proviso that if X1 is a fluoro group, then X2 should not be a bromo group; and X3 and X4 are the same or different and each is hydrogen or a fluoro group; and Y1, Y2, Y3, Y4, Y5 and Y6 are the same or different groups and each is hydrogen or a fluoro, bromo, chloro, or methyl group. The compounds (I) are insecticidally active.
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- Process for the preparation of 3-phenoxy-benzaldehydes
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In a process for the preparation of 3-phenoxy-benzaldehyde by oxidation of 3-phenoxy-benzyl alcohol of the formula STR1 in which m represents a number from 1 to 4, n represents a number from 1 to 5 and R1 and R2 are identical or different and denote hydrogen, halogen, alkyl, cycloalkyl, aralkyl, alkoxy, cycloalkoxy, aryloxy or perfluoroalkyl, with an oxygen containing gas in aqueous alkali at a temperature from the solidification point to the boiling point of the reaction mixture in the presence of a platinum metal catalyst and in the presence of lead and/or bismuth and/or tellurium and/or a compound of said lead, bismuth or tellurium.
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- Process for the preparation of 3-phenoxybenzenes
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3-Phenoxybenzene derivatives are prepared by a method which comprises the steps of(a) chlorinating benzaldehyde with chlorine gas in the presence of a hydrocarbon and a Lewis acid catalyst to obtain 3-chlorobenzaldehyde; (b) reacting the 3-chlorobenzaldehyde with ethylene glycol to obtain 2-(3-chlorophenyl)-1,3-dioxolane; (c) etherifying said dioxolane with an alkali phenolate to yield the intermediate 2-(3-phenoxyphenyl)-1,3-dioxolane and converting this intermediate to the corresponding aldehyde, cyanohydrin, sulfonic acid salt or oxime derivative.
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- Process for preparing m-phenoxybenzylalcohol and side-chain halogenated m-phenoxytoluene
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A process for preparing m-phenoxybenzyl, m-phenoxybenzal halides or a mixture thereof comprising halogenating m-phenoxytoluene in the presence of a phosphorus halide in the high temperature region above 220° C, and a process for preparing m-phenoxybenzylalcohol comprising halogenating m-phenoxytoluene as above, reacting the resulting side-chain halogenated m-phenoxytoluene with an alkali metal salt of acetic acid and then (a) reducing and hydrolyzing the resulting m-phenoxybenzylacetate and m-phenoxybenzaldehyde, or (b) reducing the resulting m-phenoxybenzylacetate and m-phenoxybenzaldehyde, reacting the resulting product with acetic anhydride and an alkali metal salt of acetic acid and hydrolyzing the resulting m-phenoxybenzylacetate are disclosed.
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- Process for the preparation of carbinols
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Organic compounds containing a carboxylic acid or carboxylic acid anhydride group are reduced when contacted with an alkali metal borohydride and a boron trihalide in a liquid medium in which diborane is soluble in the form of a labile borane adduct. Hydrolysis of the reaction mixture then provides a useful synthesis of the corresponding carbinols. The alkali metal borohydride-boron trihalide reagent may either be preformed and reacted subsequently with an organic compound containing a carboxylic acid or anhydride group, or the alkali metal borohydride-boron trihalide reagent may be produced in the presence of an organic compound containing a carboxylic acid or anhydride group. This development makes it possible to synthesize a wide variety of carbinols which are valuable and useful intermediates in organic synthesis.
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