- Para -Selective hydroxylation of alkyl aryl ethers
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para-Selective hydroxylation of alkyl aryl ethers is established, which proceeds with a ruthenium(ii) catalyst, hypervalent iodine(iii) and trifluoroacetic anhydride via a radical mechanism. This protocol tolerates a wide scope of substrates and provides a facile and efficient method for preparing clinical drugs monobenzone and pramocaine on a gram scale.
- Zhu, Runqing,Sun, Qianqian,Li, Jing,Li, Luohao,Gao, Qinghe,Wang, Yakun,Fang, Lizhen
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supporting information
p. 13190 - 13193
(2021/12/16)
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- Campestarenes: New building blocks with 5-fold symmetry
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Campestarene is a planar, shape-persistent macrocycle with 5-fold symmetry. A range of derivatives bearing peripheral functional groups suitable for generating supramolecular interactions has been designed and synthesised for potential applications in creating 2D quasicrystal molecular assemblies. The new campestarene derivatives bear ester, carboxylic acid, methoxy, bromo, 4-pyridyl, 4-cyanophenyl and 4-phenyl carboxylic acid groups, including further derivatives of the latter two bearing alkyl chains on the phenyl groups to improve solubility. The campestarene derivatives were prepared by reductive condensation of phenol precursors bearing nitro and formyl groups using Na2S2O4. The target functional groups were installed either by pre-cyclisation derivatisation or by synthesis of methoxy-substituted campestarene and subsequent derivatisation. The cyclisation reaction is tolerant of the functional groups introduced. The ten new campestarene derivatives were characterised by NMR spectroscopy and MALDI-TOF MS, although the poor solubility of some examples precluded their detailed characterisation.
- Nam, Seong,Ware, David C.,Brothers, Penelope J.
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p. 6460 - 6469
(2018/10/02)
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- Resolution of (R, S)-ethyl-2-(4-hydroxyphenoxy) propanoate using lyophilized mycelium of Aspergillus oryzae WZ007
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The mycelium of Aspergillus oryzae WZ007 was successfully developed to kinetic resolution of (R, S)-ethyl-2-(4-hydroxyphenoxy) propanoate ((R, S)-EHPP) for production of (R)-ethyl-2-(4-hydroxyphenoxy) propanoate ((R)-EHPP). The key biocatalytic process parameters (pH, temperature, rotation speed and substrate concentration) were optimized. Under the optimum conditions, the optical purity of (R)-EHPP was improved up to >99% when the conversion was above 49%. A. oryzae WZ007 whole-cell lipase exhibited high reaction capacity, enantioselectivity and good reusability. The tolerable substrate concentration was 0.5 mol/L, and dry mycelium of A. oryzae WZ007 maintains over 80% of its initial activity after eight repeating cycles. Therefore the enzymatic preparation of (R)-EHPP route was suitable for industrial application.
- Zheng, Jian-Yong,Wu, Jia-Yu,Zhang, Yin-Jun,Wang, Zhao
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- PPAR AGONIST COMPOUNDS, PREPARATION AND USES
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The present invention relates to novel PPAR agonist compounds as well as pharmaceutical compositions containing them. The compounds according to the invention are of quite particular therapeutic interest, notably for treating diabetes and/or dyslipidemias, as well as for preventing cardiovascular pathologies.
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Page/Page column 20
(2011/08/22)
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- Synthesis and herbicidal activity of novel pyrimidinyl derivatives containing an α-amino phosphonate moiety
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In order to find novel pyrimidinyl carboxylic acid analogs with high activity and low toxicity, a series of novel pyrimidinyl derivatives containing an -amino phosphonate moiety 5 was synthesized by the condensation of 4-(4,6-dimethoxypyrimidin-2-yloxy)phenoxyacetic 3a or propionic acids 3b with dialkyl -amino substitutedbenzyl phosphonates 4. Their structures were characterized by spectroscopic data (IR, 1H NMR, 31P NMR, MS) and elemental analyses. The results of preliminary herbicidal activities (in vitro) showed that most of these compounds exhibited higher herbicidal activities against dicotyledonous weeds (Brassica campestris L) than monocotyledonous weeds (Echinochloa crus-galli). Further bioassays (in vivo) indicated that some of compounds 5 possessed selective herbicidal activity against amaranth pigweed (A. retroflexus) in post-emergence treatment. Copyright Taylor & Francis Group, LLC.
- Yu, Zhi-Hua,Shi, De-Qing
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experimental part
p. 2316 - 2323
(2011/01/12)
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- More toxic and photoresistant products from photodegradation of fenoxaprop-p-ethyl
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The photodegradation pathway of the commonly used herbicide fenoxaprop-p-ethyl (FE) was elucidated, and the effects of the photodegradation on its toxicity evolution were investigated. Under solar irradiation, FE could undergo photodegradation, and aceton
- Lin, Jing,Chen, Jingwen,Wang, Ying,Cai, Xiyun,Wei, Xiaoxuan,Qiao, Xianliang
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experimental part
p. 8226 - 8230
(2010/03/30)
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- A novel synthesis and herbicidal activity of fluorine-containing pyrazolo[3,4-d]pyrimidin-4-one derivatives
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The 6-(4-alkoxycarbonylalkoxy)phenoxy-3-alkylthio-5-(fluoro-substituted)phenyl-1-phenylpyrazolo[3,4-d]pyrimidin-4-ones 6 have been successfully synthesized via a tandem aza-Wittig and annulation reactions of the corresponding iminophosphorances 4, aromatic isocyanate, and substituted phenols 2 in 59-69% isolated yields using actonitrile as solvent. These novel compounds 6 could be oxidized to sulfones 7 by hydrogen peroxide in satisfactory yields (57-93%). Their structures were clearly verified by spectroscopic data (IR, 1H NMR, 13C NMR, MS, Elemental analysis or X-ray diffraction crystallography). The results of preliminary bioassay indicated that these compounds possess herbicidal activity against the root of rape and barnyard grass.
- Liu, Hui,Wang, Hong-Qing,Ding, Ming-Wu,Liu, Zhao-Jie,Xiao, Wen-Jing
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p. 1584 - 1590
(2008/09/18)
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- Synthesis and immunosuppressive activity of new artemisinin derivatives. 1. [12(β or α)-dihydroartemisininoxy]phen(ox)yl aliphatic acids and esters
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A series of novel dihydroartemisinin derivatives were synthesized and evaluated on their immunosuppressive activity in the search for potential immunosuppressive agents with high efficacy and low toxicity. These compounds were assayed in their cytotoxicity of lymphocyte, inhibition activity on concanavalin A (ConA) induced T cell proliferation and lipopolysaccharide (LPS) induced B cell proliferation. Among them, 11b, 13b, 14d, 15b, 16, and 17 remarkably exhibited lower cytotoxicity and higher inhibition activity on the mitogen-induced T cell and B cell proliferation in comparison with artemisinin, artesunate, and artemether in vitro. More significantly, compound 11b displayed reduced cytotoxicity by over 100-fold compared with cyclosporin A (CsA) and comparable inhibition activity (SI = 848) on ConA-induced T cell proliferation to CsA (SI = 963) and more than 4000 times the inhibitory effect (SI = 28473) on LPS-induced B cell proliferation compared with CsA (SI = 7) in vitro. The in vivo experimental results showed that compound 16 could inhibit 2,4-dinitrofluorobenzene (DNFB)-induced delayed-type hypersensitivity (DTH) reaction and sheep red blood cell (SRBC) induced antibody production, respectively. The structure and activity relationships (SAR) of these compounds were also discussed.
- Yang, Zhong-Shun,Zhou, Wen-Liang,Sui, Yi,Wang, Jun-Xia,Wu, Jin-Ming,Zhou, Yu,Zhang, Yu,He, Pei-Lan,Han, Ji-Ye,Tang, Wei,Li, Ying,Zuo, Jian-Ping
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p. 4608 - 4617
(2007/10/03)
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- Microbial deracemization of α-substituted carboxylic acids: Substrate specificity and mechanistic investigation
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A new enzymatic method for the preparation of optically active α-substituted carboxylic acids is reported. This technique is called deracemization reaction, which provides us with a route to obtain the enantiomerically pure compounds, theoretically in 100% yield starting from the racemic mixture. This means that the synthesis of a racemate is almost equal to the synthesis of the optically active compound, and this concept is entirely different from the commonly accepted one in the asymmetric synthesis. Using the growing cell system of Nocardia diaphanozonaria JCM3208, racemates of 2-aryl- and 2-aryloxypropanoic acid are deracemized smoothly and (R)-form-enriched products are recovered in high chemical yield (>50%). In addition, using optically active starting compounds and deuterated derivatives as well as inhibitors, we have disclosed the fact that a new type of enzyme takes part in this biotransformation, and that the reaction proceeds probably via the same mechanism as that in rat liver.
- Kato, Dai-Ichiro,Mitsuda, Satoshi,Ohta, Hiromichi
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p. 7234 - 7242
(2007/10/03)
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- Design, synthesis, and evaluation of postulated transient intermediate and substrate analogues as inhibitors of 4-hydroxyphenylpyruvate dioxygenase
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An epoxybenzoquinone, 4-hydroxyphenoxypropionic acid, and 2-hydroxy-3-phenyl-3-butenoic acid derivatives have been designed, synthesized, and evaluated for in vitro inhibition activity against 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) from pig liver by the spectrophotometric enol-borate method. The biological data demonstrated that neither epoxybenzoquinone ester nor 2-hydroxy-3-phenyl-3-butenoic acid is an inhibitor of 4-HPPD. The most potent 4-HPPD inhibitor tested was 3-hydroxy-4-phenyl-2(5H)-furanone with an IC50 value of 0.5 μM, which may serve as a lead compound for further design of more potent 4-HPPD inhibitors.
- Lin, Yun-Loung,Huang, Jian-Lin,Wu, Chung-Shieh,Liu, Hung-Ge,Yang, Ding-Yah
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p. 1709 - 1713
(2007/10/03)
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- Evaluation of the Elbs Persulfate Oxidation Reaction for the Preparation of Aryloxyphenoxypropionate Herbicides
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A new, simple method for the preparation of several 4-(aryloxy)phenols (2a-d) and alkyl 2-(4-hydroxyphenoxy)propionates (3a,b) is described.These compounds are key precursors for the synthesis of important aryloxyphenoxypropionate herbicides (1a-d).The method uses the Elbs persulfate oxidation to convert phenol into 4-hydroxyphenyl sulfate (5).The free hydroxy group is then reacted with various aryl halides and alkyl 2-halopropionates.Mild hydrolysis of the sulfate group with boiling acetic acid then gives the products (2a-d) and (3a,b), generally in modest to good yield.
- Watson, Keith G.,Serban, Alexander
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p. 1503 - 1510
(2007/10/02)
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- Heterocyclic oxy-phenoxyacetic acid derivatives and their use as herbicides
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A heterocyclic oxy-phenoxyacetic acid derivative of the formula: STR1 , or its salt, which is useful as a herbicide.
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- Process for producing ethyl 2-[4'-(6"-chloro-2"-benzoxazolyloxy)phenoxy]propionate
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A method for producing ethyl 2-[4'-(6"-chloro-2"-benzoxazolyloxy)phenoxy]propanoate by reacting a hydroxyaromatic ketone derivative with a 2-substituted propanoic ester under basic conditions and thereafter oxidizing the intermediate with subsequent hydrolysis and reaction with 2,6-dichlorobenzoxazole.
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- Herbicidally active phenoxyalkanecarboxylic acid derivatives
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A compound of the formula: STR1 wherein Q1 is CH or N; R is H or C1 -C5 alkyl; X is H, halogen, CF3, or NO2 ; Y is H or halogen; Z is --O-- or --NH--; A is STR2 wherein Q2, and Q3 are each CH or N; R1 and R2 are each H, C1 -C5 alkyl, C1 -C5 alkoxy, or C2 -C6 alkxoycarobnyl; R3, R4, and R5 are each H or C1 -C5 alkyl; R6 is H, halogen, or C1 -C5 alkyl; R7, R8, R9, and R10 are each H or C1 -C5 alkyl; R11 is H, C1 -C5 alkyl, C1 -C5 alkoxy, C2 -C6 alkenyl, C6 -C10 aryl, C7 -C15 aryloxyalkyl, or C7 -C15 aralkyl; R12 and R13 are each H or C1 -C5 alkyl; R14 is C1 -C5 alkyl, C2 -C6 alkenyl, C5 -C10 aryl, or C7 -C15 aralkyl; or R13 and R14 taken together form C3 -C4 alkylene, V1 and V2 are each H, halogen, NO2, CN, or CF3 ; V3 is halogen or CF3 ; W1 is --O-- or --NH--; W2 is --(CH2)n -- wherein n is 0 or 1, or CO; X1 is halogen, or a salt thereof, which is effective as a herbicidal agent.
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- Process for the synthesis of phenoxyalkane derivatives
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The invention concerns a process for the synthesis of a compound of formula I STR1 wherein: U and V may be chosen from a range of substituents including hydrogen, halogen, alkyl and alkoxy; R1 and R2 may be chosen from a range of substituents including hydrogen and alkyl; n is 0, 1 or 2; and W may be chosen from a range of substitutents including the group STR2 which may be a free carboxylic acid or derivative thereof; the process comprising reacting a sulfate ester of formula II, wherein Q is a cation, with a compound of formula III, wherein L is a leaving group STR3 and hydrolyzing the sulfate ester formed. Preferably the sulfate ester of formula II is prepared by the oxidation of a phenol of formula IV with a persulfate. STR4
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- Process for preparing 2-(4-hydroxyphenoxy) alkanoic acid compounds
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A process for preparing a 2-(4-hydroxyphenoxy) alkanoic acid, its ester or alkali metal salt, or an optical isomer thereof, which comprises condensing hydroquinone or an alkali metal salt of hydroquinone with a compound having the formula: STR1 wherein X is a p-toluenesulfonyl group, a methanesulfonyl group, a benzylsulfonyl group, a p-chlorobenzenesulfonyl group or a benzenesulfonyl group, R1 is a hydrogen atom or a lower alkyl group, and R2 is a hydrogen atom, an alkyl group or an alkali metal cation, or its optical isomer in the presence of a base.
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- Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds
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A process for preparing an optically active 2-(4-hydroxyphenoxy)propionic acid compound, which comprises reacting an optically active compound having the formula: STR1 wherein X is a chlorine atom or a bromine atom, and M is a hydrogen atom or an alkali metal atom, with hydroquinone or an alkali metal salt of hydroquinone, in the presence of an alkali metal hydroxide and water, and precipitating optically active disodium 2-(4-hydroxyphenoxy)propionate.
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- Process for producing 2-(4-hydroxyphenoxy) propionate derivatives
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A process for producing a 2-(4-hydroxyphenoxy) propionate derivative represented by the formula: STR1 where Alk is a C1 -C5 alkyl group, which comprises reacting a phenoxy propionate derivative represented by the formula: STR2 where Alk is as defined above, with a peroxide to obtain a formate derivative represented by the formula: STR3 where Alk is as defined above, and hydrolyzing the formate of the formula III.
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- Preparation of 2-(hydroxyphenoxy)-carboxylates
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2-(Hydroxyphenoxy)-carboxylates are prepared by a process wherein a dihydroxybenzene (A) is reacted with a 2-halo-fatty acid ester (B) of an alcohol, phenol or oxime of no more than 10 carbon atoms, in a molar ratio of A:B≥1.5, in the presence of calcium hydroxide in dimethylsulfoxide, at from 0° to 100° C.
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- Derivatives of (pyrimidyloxy)phenoxy-alkanecarboxylic acid and herbicidal compositions thereof
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A compound of general formula I: STR1 wherein A, B, D, E, and V are independently chosen from hydrogen, halogen, nitro, cyano, thiocyano, amino, alkyl, alkoxy, alkylthio, alkenyl, cycloalkyl, carbalkoxy, phenyl, phenoxy or phenylthio; R1 and R2 are independently hydrogen, alkyl, alkenyl, alkanoyl, or R1 and R2 together are alkylidene; W is carboxy or a functional derivative thereof or CH2 Z wherein Z is halogen, hydroxy, alkoxy, alkylthio, formyl or amino; and X and Y are oxygen or sulfur.
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