- Selective Oxidation of Alkylarenes to the Aromatic Ketones or Benzaldehydes with Water
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Here a palladium-catalyzed oxidation method for converting alkylarenes into the aromatic ketones or benzaldehydes with water as the only oxygen donor is reported. This C-H bond oxidation functionalization does not require other oxidants and hydrogen accep
- Du, Jihong,Duan, Baogen,Liu, Kun,Liu, Renhua,Yu, Feifei,Yuan, Yongkun,Zhang, Chenyang,Zhang, Jin
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supporting information
(2022/02/09)
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- AN IMPROVED AND COMMERCIALLY VIABLE PROCESS FOR PREPARATION OF ARYL KETONES
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The present disclosure provides a process for preparing an aryl ketone of Formula I, comprising reacting a substituted benzene of Formula II with a carboxylic acid of formula IIIa and/or a carboxylic anhydride of formula IIIb in presence of an alkyl sulfonic acid acting as catalyst cum solvent/contacting medium. I, II, IIIa, IIIb, wherein, R1, R2, R3 and R4 are as defined in the description.
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Paragraph 0086-0087
(2020/09/12)
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- A molybdenum based metallomicellar catalyst for controlled and chemoselective oxidation of activated alcohols in aqueous medium
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A surfactant based oxodiperoxo molybdenum complex, which could activate molecular oxygen, has been employed as a catalyst for controlled oxidation of benzylic alcohols to corresponding carbonyls. The oxidation reactions were carried out under aqueous environment, however, in the absence of any extraneous base or co-catalyst. Sensitive/oxidizable functional groups like cyano, sulfide, hydroxyl, aryl-hydroxyl, alkene (internal/terminal), alkyne (internal/terminal), and acetal were tolerated during the transformations. Such selectivity is attributed to the mild nature of the catalyst. The methodology could also be scaled-up for multi-gram synthesis and the protocol is likely to find practical use since it requires an inexpensive recyclable-catalyst and easily available oxidant (under green conditions). A plausible mechanism is proposed with the help of preliminary computational study.
- Thiruvengetam, Prabaharan,Chakravarthy, Rajan Deepan,Chand, Dillip Kumar
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p. 123 - 133
(2019/07/19)
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- A new generation of ferrociphenols leads to a great diversity of reactive metabolites, and exhibits remarkable antiproliferative properties
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Organometallic compounds bearing the redox motif [ferrocenyl-ene-phenol] have very promising antiproliferative properties which have been further improved by incorporating pertinent substituents able to engender new mechanisms. Here we show that novel ferrociphenols bearing a hydroxypropyl chain exhibit strong antiproliferative effects, in most cases much better than those of cisplatin, tamoxifen, or of previously described ferrociphenols devoid of this terminal OH. This is illustrated, in the case of one of these compounds, by its IC50 values of 110 nM for MDA-MB-231 triple negative breast cancer cells and of 300 nM for cisplatin-resistant A2780cisR human ovarian cancer cells, and by its GI50 values lower than 100 nM towards a series of melanoma and renal cancer cell lines of the NCI-60 panel. Interestingly, oxidative metabolism of these hydroxypropyl-ferrociphenols yields two kinds of quinone methides (QMs) that readily react with various nucleophiles, such as glutathione, to give 1,6- and 1,8-adducts. Protonation of these quinone methides generates numerous reactive metabolites leading eventually to many rearrangement and cleavage products. This unprecedented and fully characterized metabolic profile involving a wide range of electrophilic metabolites that should react with cell macromolecules may be linked to the remarkable profile of antiproliferative activities of this new series. Indeed, the great diversity of unexpected reactive metabolites found upon oxidation will allow them to adapt to various situations present in the cancer cell. These data initiate a novel strategy for the rational design of anticancer molecules, thus opening the way to new organometallic potent anticancer drug candidates for the treatment of chemoresistant cancers.
- Wang, Yong,Dansette, Patrick M.,Pigeon, Pascal,Top, Siden,McGlinchey, Michael J.,Mansuy, Daniel,Jaouen, Gérard
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- Synthetic method for ultraviolet absorbent namely 4,4'-dihexyloxybenzophenone
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The invention discloses a synthetic method for an ultraviolet absorbent namely 4,4'-dihexyloxybenzophenone. The method comprises the following steps: with p-hydroxybenzoic acid as a starting material, carrying out acetylation to protect hydroxy; carrying out a Fredel-Crafts reaction of p-acetoxybenzoic acid and phenol under the catalysis of zinc chloride and phosphorus oxychloride so as to synthesize an intermediate namely phenyl p-hydroxybenzoate; then carrying out deacetylation to remove the protective group, and carrying out Fries rearrangement so as to prepare an intermediate namely 4,4-dihydroxybenzophenone; and forming a salt with 4,4-dihydroxybenzophenone and potassium carbonate, and carrying out a Williamson reaction of 1-bromohexane and the potassium salt of 4,4-dihydroxybenzophenone through catalysis of tetrabutylammonium bromide so as to synthesize the 4,4'-dihexyloxybenzophenone. The synthetic method provided by the invention has the advantages of mild reaction conditions, normal pressure, medium and low temperature, stable quality control, high raw material conversion rate, effective inhibition of side reactions, fewer three wastes, light pollution, and facilitation of protecting the environment and labor of a producer.
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Paragraph 0021; 0026; 0031; 0036; 0041
(2017/09/13)
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- Organometallic Antitumor Compounds: Ferrocifens as Precursors to Quinone Methides
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The synthesis and chemical oxidation profile of a new generation of ferrocifen derivatives with strong antiproliferative behavior in vitro is reported. In particular, the hydroxypropyl derivative HO(CH2)3C(Fc)=C(C6H4OH)2 (3 b) exhibited exceptional antiproliferative activity against the cancer cell lines HepG2 and MDA-MB-231 TNBC, with IC50 values of 0.07 and 0.11 μM, respectively. Chemical oxidation of 3 b yielded an unprecedented tetrahydrofuran-substituted quinone methide (QM) via internal cyclization of the hydroxyalkyl chain, whereas the corresponding alkyl analogue CH3CH2-C(Fc)=C(C6H4OH)2 merely formed a vinyl QM. The ferrocenyl group in 3 b plays a key role, not only as an intramolecular reversible redox "antenna", but also as a stabilized carbenium ion "modulator". The presence of the oxygen heterocycle in 3 b-QM enhances its stability and leads to a unique chemical oxidation profile, thus revealing crucial clues for deciphering its mechanism of action in vivo.
- Wang, Yong,Pigeon, Pascal,Top, Siden,McGlinchey, Michael J.,Jaouen, Grard
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p. 10230 - 10233
(2015/09/01)
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- Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids and CO: A highly selective approach to diaryl ketones
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A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O2, which makes this method practical for further applications.
- Ren, Long,Jiao, Ning
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supporting information
p. 2411 - 2414
(2014/10/15)
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- Stimuli-responsive blue fluorescent supramolecular polymers based on a pillar[5]arene tetramer
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A tetraphenylethene-bridged pillarene tetramer with aggregation-induced emission properties forms an A4/B2-type supramolecular polymer and a gel with a symmetric neutral guest linker, showing a remarkable fluorescence emission enhancement in solution and the solid state and a good responsiveness to temperature and solvent composition. This journal is the Partner Organisations 2014.
- Song, Nan,Chen, Dai-Xiong,Qiu, Yu-Chen,Yang, Xiao-Yue,Xu, Bin,Tian, Wenjing,Yang, Ying-Wei
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supporting information
p. 8231 - 8234
(2014/07/21)
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- AIE (AIEE) and mechanofluorochromic performances of TPE-methoxylates: Effects of single molecular conformations
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Two methoxy-substituted tetraphenylethylene (TPE) derivatives, tetra(4-methoxyphenyl)ethylene (TMOE) and tetra(3,4-dimethoxyphenyl)ethylene (TDMOE), were synthesized by McMurry reaction in high yields. The nearly centrosymmetric and natural propeller shape of TMOE and TDMOE excluded intermolecular effects, such as H or J-aggregation and π-π stacking, on their AIE (AIEE) and mechanofluorochromic performance. The crystal structures of TMOE and TDMOE, and theoretical calculations proved that their emission colours are determined by single molecular conjugation. These molecules were used to investigate pure conformational effects on molecular emissions. The spectral properties of these molecules in five environments of crystal(s), THF solution, THF-water binary solution, solidified THF and amorphous states, were investigated. The crystalline to amorphous phase transition by grinding resulted in good mechanofluorochromic performances with high quantum yields and distinguishable emission change, which was further explored as anti-counterfeiting inks on banknotes.
- Qi, Qingkai,Liu, Yifei,Fang, Xiaofeng,Zhang, Yumo,Chen, Peng,Wang, Yi,Yang, Bing,Xu, Bin,Tian, Wenjing,Zhang, Sean Xiao-An
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p. 7996 - 8002
(2013/07/19)
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- PROCESS FOR DEMETHYLATING AROMATIC METHYL ETHERS USING 3 -MERCAPTOPROPIONIC ACID
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The present application discloses a process for demethylating aromatic methyl ethers by reaction with 3 -mercaptopropionic acid or salts thereof. One preferred example is the demethylation of venlafaxine forming 0 - desmethylvenlafaxine.
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Page/Page column 16
(2012/01/04)
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- Process for demethylating aromatic methyl ethers using 3-mercaptopropionic acid
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The present application discloses a process for demethylating aromatic methyl ethers by reaction with 3-mercaptopropionic acid or salts thereof. One preferred example is the demethylation of venlafaxine forming O-desmethylvenlafaxine.
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Page/Page column 10
(2012/01/03)
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- Evaluation of polyhydroxybenzophenones as α-glucosidase inhibitors
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This experiment was designed to synthesize 18 kinds of polyhydroxybenzophenones by using Friedel-Crafts reaction, and to measure the inhibitory activity on α-glucosidase with p-nitrophenyl-β-D- galactopyranoside (PNPG) as a substrate. Here, acarbose (IC50a= a1674.75aaμmolaL-1) was used as the reference inhibitor. The results demonstrated that most of the target compounds had remarkable inhibitory activities on α-glucosidase. Among all these compounds, 2,4,4′,6-butahydroxydiphenylketone (11) was found to be the most potent α-glucosidase inhibitor with an IC50 value of 10.62aaμmolaL-1. In addition, we found these compounds were competitive inhibitors through the kinetic analysis. The results suggested that such compounds might be utilized for the development of new candidates for diabetes treatment. A series of polyhydroxybenzophenones was synthesized and evaluated as α-glucosidase inhibitors. Compound 11 was found to be the most potent inhibitor. Copyright
- Hu, Xuesen,Xiao, Yang,Wu, Jianlong,Ma, Lin
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experimental part
p. 71 - 77
(2011/09/21)
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- Synthesis and biological evaluation of polyhydroxy benzophenone as mushroom tyrosinase inhibitors
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A series of polyhydroxy benzophenone were synthesized and evaluated as mushroom tyrosinase inhibitors. The results demonstrated that most of the target compounds had remarkable inhibitory activities on mushroom tyrosinase. Among all these compounds, 2,3,4,3′,4′,5′-hexahydroxy-diphenylketone 10 was found to be the most potent tyrosinase inhibitor with IC50 value of 1.4 μM. In addition, the inhibition kinetics analyzed by Lineweaver-Burk plots revealed that such compounds were competitive inhibitors. These results suggested that such compounds might be utilized for the development of new candidate for treatment of dermatological disorders.
- Wu, Jianlong,Hu, Xuesen,Ma, Lin
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experimental part
p. 449 - 452
(2012/01/04)
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- First synthesis of antitubercular natural product 2-hydroxy-5-(4- hydroxybenzyl) benzaldehyde (forkienin)
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The synthesis of 2-hydroxy-5-(4-hydroxybenzyl)benzaldehyde an antitubercular compound, from the readily available starting compound p-hydroxybenzoic acid in 4 steps is described.
- Singh, Ashima,Sharma,Singh, Jasvinder
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experimental part
p. 148 - 149
(2009/04/07)
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- High-yielding cleavage of (aryloxy)acetates
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A reliable and high-yielding one-pot sequence for the removal of O-carboxymethyl moieties from phenols is presented. When diethylphosphoryl azide is employed as the azide transfer reagent in the Curtius rearrangement and glycerol in the subsequent hydrolytic workup, the protocol can be reliably applied to a very broad scope of substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Spurg, Anke,Waldvogel, Siegfried R.
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p. 337 - 342
(2008/09/18)
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- 2-(Diethylamino)ethanethiol, a new reagent for the odorless deprotection of aromatic methyl ethers
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A new reagent for the deprotection of aromatic methyl ethers, 2-(diethylamino)ethanethiol, is reported. This compound, commercially available as its HCl salt, affords the corresponding phenols in good to excellent yields on a wide variety of substrates. A clear advantage of this method over the use of more common thiols, such as ethanethiol, is the easy extraction of both the deprotecting reagent and the byproduct 2-(diethylamino)ethyl methyl sulfide into the aqueous phase by quenching with dilute acid, which allows an essentially odorless workup.
- Magano, Javier,Chen, Michael H.,Clark, Jerry D.,Nussbaumer, Thomas
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p. 7103 - 7105
(2007/10/03)
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- Method for producing 4-amino-5-chloro-1-phenyl pyridazinone-(6)
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In a process for preparing 4-amino-5-chloro-1-phenylpyridazin-6-one by reacting 4,5-dichloro-1-phenylpyridazin-6-one with aqueous ammonia in the presence of a catalyst, the catalyst used is soluble in the aqueous alkaline reaction medium but is essentially insoluble in the reaction medium which has been acidified after removal of the 4-amino-5-chloro-1-phenylpyridazin-6-one. The process of the present invention makes it possible for the catalyst to be recovered and reused in a simple manner.
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- Polymer electrolyte and process for producing the same
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A polymer electrolyte having, in a main chain, a structural unit represented by the following formula (1):-[Ar1-(SO2-N-(X+)-SO2-Ar2)m-SO2-N-(X+)-SO2-Ar1-O]- wherein Ar1 and Ar2 independently represent a divalent aromatic groups, m represents an integer of 0 to 3, and X+ represents an ion selected from hydrogen ion, an alkali metal ion and ammonium ion, which is excellent in proton conductivity, thermal resistance and strength. The polymer electrolyte is soluble in solvents and has excellent film forming property and recycling efficiency.
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- Hydroxylation of phenolic compounds
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Phenolic compounds, e.g., the phenols and phenol ethers, are selectively hydroxylated whereby the amounts of the final product para isomer are enhanced, for example in favor of hydroquinone versus pyrocatechol in the event of the hydroxylation of phenol, by reacting such phenolic compounds with hydrogen peroxide, advantageously in a polar, aprotic, organic solvent reaction medium, in the presence of a catalytically effective amount of a sulfonated polymer and a cocatalytically effective amount of an aromatic ketone compound.
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- Hydroxylation of phenolic compounds
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Phenolic compounds, e.g., phenol, are hydroxylated, preponderantly into the para-isomer, e.g., hydroquinone, by reaction with hydrogen peroxide in the presence of an effective amount of a strong acid and a catalytically effective amount of a keto compound having the formula (II): STR1 in which R1 and R2, which may be identical or different, are each a hydrogen atom or an electron-donating group; n1 and n2, which may be identical or different, are numbers equal to 0, 1, 2 or 3, with the proviso that the two carbon atoms located at the α-position with respect to the two carbon atoms bearing the --CO group may be bonded together via a valence bond or via a --CH2 -- group, thereby forming a keto-containing ring member which may either be saturated or unsaturated.
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- Method for preparing aromatic bischloroformate compositions
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Bischloroformate oligomer compositions are prepared by passing phosgene into a heterogeneous aqueous-organic mixture containing at least one dihydroxyaromatic compound, with simultaneous introduction of a base at a rate to maintain a specific pH range and to produce a specific volume ratio of aqueous to organic phase. By this method, it is possible to employ a minimum amount of phosgene. The reaction may be conducted batchwise or continuously. The bischloroformate composition may be employed for the preparation of cyclic polycarbonate oligomers or linear polycarbonate, and linear polycarbonate formation may be integrated with bischloroformate composition formation in a batch or continuous process.
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- Bischoloroformate preparation method with phosgene removal and monochloroformate conversion
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Aqueous bischloroformates are prepared by the reaction of a dihydroxyaromatic compound (e.g., bisphenol A) with phosgene in a substantially inert organic liquid (e.g., methylene chloride) and in the presence of an aqueous alkali metal or alkaline earth metal base, at a pH below about 8. After all solid dihydroxyaromatic compound has been consumed, the pH is raised to a higher value in the range of about 7-12, preferably 9-11, and maintained in said range until a major proportion of the unreacted phosgene has been hydrolyzed. At the same time, any monochloroformate in the product may be converted to bischloroformate.
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- Cyclic monocarbonate bishaloformates
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Cyclic monocarbonate bischloroformates are prepared by the reaction of a carbonyl halide such as phosgene with a bridged substituted resorcinol or hydroquinone such as bis(2,4-dihydroxy-3-methylphenyl)methane or bis(2,5-dihydroxy-3,4,6-trimethylphenyl)methane in the presence of aqueous alkali metal hydroxide. The cyclic monocarbonate bischloroformates may be used for the preparation of linear or cyclic polycarbonates containing cyclic carbonate structural units, which may in turn be converted to crosslinked polycarbonates.
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- Polyetherimide bisphenol compositions
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Polyetherimide bisphenols and bischloroformates are prepared by the reaction of dianhydrides or certain bisimides with aminophenols or mixtures thereof with diamines. They are useful as intermediates for the preparation of cyclic heterocarbonates, which may in turn be converted to linear copolycarbonates. The bisphenols can also be converted to salts which react with cyclic polycarbonate oligomers to form block copolyetherimidecarbonates.
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- Production of hydroxy arylophenones
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Production of a hydroxy arylophenone by reacting an aromatic carboxylic acid Ar(--CO2 H)p where Ar is an aromatic radical, (--CO2 H) is an aromatic carboxylic acid group, and p is 1 or 2 with an aromatic compound H--Ar'--OH where Ar' is an aromatic radical and --H and --OH are aromatically bound para to each other in a benzenoid ring, in the presence of an alkyl sulphonic acid, particularly methane sulphonic acid, to produce a hydroxy arylophenone of formula Ar(--CO--Ar'--OH)p where the carbonyl and hydroxyl groups are para to each other in the hydroxyl-containing benzenoid ring of Ar'. The production of the hydroxy arylophenone proceeds through the intermediate ester (H--Ar'--O--CO--)p Ar and the production of the hydroxy arylophenone starting from the ester is also claimed.
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