- Hydroformylation of natural olefins with the [Rh(COD)(μ-OMe)]2/TPPTS complex in BMI-BF4/toluene biphasic medium: Observations on the interfacial role of CTAB in reactive systems
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The complex [Rh(COD)(μ-OMe)]2 in presence of TPPTS (TPPTS = triphenylphosphinetrisulfonate) was evaluated as catalyst precursor for the in situ hydroformylation of natural olefins (eugenol, estragole and safrole) in biphasic media BMIm-BF4/toluene. Under moderate reaction conditions, the substrates showed the following reactivity order: eugenol > estragole > safrole. The rhodium system showed a high activity and selectivity towards the desired aldehydes. It was found that the use of cetyltrimethylammoniun bromide (CTAB) as phase transfer agent inhibits the hydroformylation reaction. The catalytic phase can be recycled up to four times without evident loss of activity or selectivity. In this work we report the use of an ionic liquid with hydrophilic character, without using water in the reaction medium.
- Baricelli, Pablo J.,Borusiak, Margarita,Crespo, Isis,Melean, Luis G.,Pereira, Juan C.,Rodríguez, Mariandry,Rosales, Merlín
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- Biphasic hydroformylation of substituted allylbenzenes with water-soluble rhodium or ruthenium complexes
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The water-soluble complexes [Rh(CO)(Pz)(L)]2 and [HRu(CO)(CH3CN)(L)3][BF4] [L = TPPMS (m-sulfonatophenyl-diphenylphosphine) and TPPTS (tris-m-sulfonato- phenylphosphine)] were used for the first time as catalyst precursors for the hydroformylation of eugenol, estragole, safrole and trans-anethole under moderate conditions in biphasic media. Under mild reaction conditions the substrates showed the following reactivity order: eugenol > estragole ≈ safrole > trans-anethole. The use of cetyl-trimethylammonium chloride (CTAC) as phase transfer agent inhibits the isomerization reaction, reaching high selectivity for the hydroformylation products (80-94%). The catalytic phase can be recycled up to four times with a decrease in the activity over time but maintaining its high selectivity.
- Melean, Luis G.,Rodriguez, Mariandry,Romero, Marynell,Alvarado, Maria L.,Rosales, Merlin,Baricelli, Pablo J.
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- Bioreduction of α-methylcinnamaldehyde derivatives: Chemo-enzymatic asymmetric synthesis of Lilial and Helional
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Nonracemic aryl-substituted α-methyldihydrocinnamaldehyde derivatives employed as olfactory principles in perfumes (Lilial, Helional) were obtained via enzymatic reduction of the corresponding cinnamaldehyde precursors using cloned and overexpressed ene-reductases. (R)-Enantiomers were obtained using the old-yellow-enzyme (OYE) homolog YqjM from Bacillus subtilis and 12-oxophytodienoic acid reductase isoenzyme OPR1 from tomato (e.e. max 53%), and (S)-aldehydes were furnished in up to 97% e.e. using isoenzyme OPR3, nicotinamide 2-cyclohexene-1-one reductase NCR from Zymomonas mobilis and yeast OYE isoenzymes 1-3 under optimised reaction conditions in the presence of t-butyl methyl ether as the co-solvent. The stereochemical outcome of the reduction of α-methylcinnamaldehyde using NCR and OYEs 1-3 [previously reported to be (R)] was unambiguously corrected to be (S).
- Stueckler, Clemens,Mueller, Nicole J.,Winkler, Christoph K.,Glueck, Silvia M.,Gruber, Karl,Steinkellner, Georg,Faber, Kurt
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- Arylation of β-methallyl alcohol catalyzed by Pd(OAc)2 in combination with P(t-Bu)3: application to fragrance synthesis
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Pd(OAc)2 in combination with P(t-Bu)3 catalyzes the coupling of β-methallyl alcohol with 1-bromo-3,4-(methylenedioxy)benzene (1a), 1-bromo-4-methoxybenzene (1b), or 1-bromo-4-tert-butylbenzene (1c). The reaction affords the corresponding 2-methyl-3-aryl-propanals, which are valuable floral fragrances. With 1a or 1b high reaction rates are obtained at 130 °C using NMP/water mixtures and an inorganic base such as Na2CO3. The chemoselectivity of the reaction is almost complete, so that the process appears practically feasible. In contrast, the coupling of β-methallyl alcohol with 1c proceeds with low reaction rates.
- Scrivanti, Alberto,Bertoldini, Matteo,Beghetto, Valentina,Matteoli, Ugo
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- Synthesis method of helional
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The invention relates to a synthesis method of helional, and belongs to the technical field of organic synthesis. According to the synthesis method of helional, the method comprises the following step: at the reaction temperature of 60-80 DEG C, in a reaction kettle provided with rising microbubbles, carrying out catalytic reaction by taking methylacrolein and benzodioxole as raw materials and taking Bronsted acid as a catalyst to synthesize the helional in one step. The chemical reaction formula is shown in the specification. The synthesis method of the helional can be carried out under low pressure or normal pressure. In the method, inert gas and gaseous methylacrolein are mixed according to a specific proportion, and the mixed gas is pumped into a reactor filled with benzodioxole through the reinforced microbubble reactor, so that methylacrolein and benzodioxole react quickly, and side reaction caused by unstable methylacrolein is avoided. In the conventional method, methylacrolein needs to react with acetic anhydride for protection, and then react with benzodioxole for deprotection, and thus chemical wastes are generated.
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Paragraph 0018; 0035-0050
(2021/10/16)
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- Catalytic Selective Oxidative Coupling of Secondary N-Alkylanilines: An Approach to Azoxyarene
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Azoxyarenes are among important scaffolds in organic molecules. Direct oxidative coupling of primary anilines provides a concise fashion to construct them. However, whether these scaffolds can be prepared from secondary N-alkylanilines is not well explored. Here, we present a catalytic selective oxidative coupling of secondary N-alkylaniline to afford azoxyarene with tungsten catalyst under mild conditions. In addition, azoxy can be viewed as a bioisostere of alkene and amide. Several "azoxyarene analogues" of the corresponding bioactive alkenes and amides showed comparable promising anticancer activities.
- Ke, Lei,Zhu, Guirong,Qian, Hui,Xiang, Guangya,Chen, Qin,Chen, Zhilong
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supporting information
p. 4008 - 4013
(2019/06/04)
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- Asymmetric α-Allylation of Aldehydes with Alkynes by Integrating Chiral Hydridopalladium and Enamine Catalysis
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A palladium-catalyzed asymmetric α-allylation of aldehydes with alkynes has been established by integrating the catalysis of enamine and chiral hydridopalladium complex that is reversibly formed from the oxidative addition of Pd(0) to chiral phosphoric acid. The ternary catalyst system, consisting of an achiral palladium complex, a primary amine, and a chiral phosphoric acid allows the reaction to tolerate a wide scope of α,α-disubstituted aldehydes and alkynes, affording the corresponding allylation products in high yields and with excellent levels of enantioselectivity.
- Su, Yong-Liang,Li, Lu-Lu,Zhou, Xiao-Le,Dai, Zhen-Yao,Wang, Pu-Sheng,Gong, Liu-Zhu
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p. 2403 - 2406
(2018/04/27)
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- The present invention relates to a new process for the preparation of heliotropine
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The invention relates to a method for preparing helional and discloses a method which comprises steps of carrying out Claisen-Schmidt condensation reaction between heliotropin serving as a raw material and propionaldehyde under the catalysis of strong-basicity ion exchange resin, and further performing catalytic hydrogenation so as to obtain the target product. The method is characterized in that the strong-basicity ion exchange resin is used to replace other strong bases for catalyzing Claisen-Schmidt condensation reaction, the reaction yield is greatly improved, disproportionation reaction which can cause relevant impurities is avoided, and the purification is easy. The method is a route which is high in yield, low in cost, safe and applicable for industrial synthesis.
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Page/Page column 4; 5
(2017/02/17)
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- An easily recoverable and recyclable homogeneous polyester-based Pd catalytic system for the hydrogenation of α,β-unsaturated carbonyl compounds
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Abstract Homogeneous catalysis is an efficient tool to carry out hydrogenation processes but the major drawback is represented by the separation of the expensive catalyst from the product mixture. In this view we prepared a polyester-based Pd catalytic system that offers the advantages of both homogenous and heterogeneous catalyses: efficacy, selectivity and recyclability. Here its application in the hydrogenation of selected α,β-unsaturated carbonyl compounds is described.
- Bartoli, Mattia,Rosi, Luca,Petrucci, Giorgio,Armelao, Lidia,Oberhauser, Werner,Frediani, Marco,Piccolo, Oreste,Rathod, Vikas Damu,Paganelli, Stefano
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p. 228 - 233
(2015/07/20)
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- Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands
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The rhodium-catalyzed hydroformylation of eugenol was performed in aqueous biphasic systems using various water soluble phosphines: TPPTS (triphenylphosphinetrisulphonated); BDPPETS (bisdiphenylphosphinoethanetetrasulphonated), BDPPPTS (bisdiphenylphosphi
- Baricelli, Pablo J.,Rodriguez, Mariandry,Melean, Luis G.,Alonso, Maria Modroo,Borusiak, Margarita,Rosales, Merlin,Gonzalez, Beatriz,De Oliveira, Kelley C. B.,Gusevskaya, Elena V.,Dos Santos, Eduardo N.
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p. 163 - 169
(2015/05/06)
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- Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands
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The rhodium-catalyzed hydroformylation of eugenol was performed in aqueous biphasic systems using various water soluble phosphines: TPPTS (triphenylphosphinetrisulphonated); BDPPETS (bisdiphenylphosphinoethanetetrasulphonated), BDPPPTS (bisdiphenylphosphi
- Baricelli, Pablo J.,Rodriguez, Mariandry,Melean, Luis G.,Alonso, Maria Modro?o,Borusiak, Margarita,Rosales, Merlin,Gonzalez, Beatriz,De Oliveira, Kelley C. B.,Gusevskaya, Elena V.,Dos Santos, Eduardo N.
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p. 163 - 169
(2015/05/05)
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- PURIFICATION PROCESS FOR PARA-METHALLYLPYROCATECHOL
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The present invention relates to a process for the purification of para-methallylpyrocatechol and to the preparation of flavor and fragrance compounds from para-methallylpyrocatechol.
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- Simple and efficient water soluble thioligands for rhodium and iridium catalyzed biphasic hydrogenation
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The activity of catalytic systems derived from the interaction between Rh(CO)2acac and [Ir(COD)Cl]2, respectively, with the water soluble thioligands (L)-Cysteine (1) and (S)-Captopril (2), was tested in the aqueous biphasic hydrogenation of some representative α,β-unsaturated compounds as 2-cyclohexen-1-one (I), trans-cinnamaldehyde (V) and [3-(1,3-benzodioxol-5-yl)-2-methylpropenal] (X), precursor of the fragrance Helional (XI). The precatalyst Rh/Cap was able to hydrogenate cyclohexenone even at low pressure at 60 °C in a neutral medium while Rh/Cy required either higher pressure and temperature or an alkaline medium. The iridium based catalysts, Ir/Cy and Ir/Cap, showed an analogous trend though their activities were lower than those of the related rhodium catalysts. All the catalysts were easily recycled without significant loss of activity. The rhodium catalysts were also used in the hydrogenation of the above aldehydes V and X and their activity was strongly enhanced when ethylene glycol was used as organic solvent or co-solvent.
- Di Dio, Sabrina,Marchetti, Mauro,Paganelli, Stefano,Piccolo, Oreste
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scheme or table
p. 205 - 210
(2012/02/02)
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- Aqueous biphasic hydrogenations catalyzed by rhodium and iridium complexes modified with human serum albumin
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Water soluble complexes derived from the interaction between Rh(CO)2(acac) and [Ir(COD)Cl]2, respectively, with human serum albumin (HSA), were employed in the aqueous biphasic hydrogenation of α,β-unsaturated compounds as 2-cyclohexen-1-one (I), 2-butenal (V), 3-phenyl-2-propenal (IX) and 3-aryl-2-methyl-2-propenals (XIII and XVII). Both catalytic systems Rh/HSA and Ir/HSA showed to be very active in the hydrogenation of ketone I even at low temperature and hydrogen pressure; in particular, the rhodium based catalyst showed to be very selective affording exclusively cyclohexanone (II). The α,β-unsaturated aldehydes investigated required higher temperature (up to 60 °C) and pressure (5 MPa) to obtain good conversions. In this case Rh/HSA resulted to be more active than Ir based catalyst. In all cases both Rh/HSA and Ir/HSA were easily recycled without significant loss of activity.
- Marchetti, Mauro,Minello, Fabiola,Paganelli, Stefano,Piccolo, Oreste
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scheme or table
p. 76 - 80
(2010/10/02)
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- PROCESS FOR PREPARING HYDROCINNAMIC ALDEHYDES IN ENANTIOPURE OR ENANTIOMERICALLY ENRICHED FORM
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A process is described for preparing hydrocinnamic aldehydes in enantiopure or enantiomerically enriched form of Formula I, in which R is isopropyl or tert-butyl and R' is hydrogen, or R and R' when taken together are a methylenedioxolyl group, comprising the following steps: a) reacting the hydrocinnamic aldehyde of Formula I with the alcohol of Formula Il in enantiopure or enantiomerically enriched form to give the crystallized hemiacetal of Formula III, in which R, R' have the same meaning as Formula I and (*) indicates a stereogenic centre in the absence of a solvent or in one or more aprotic solvents or mixtures thereof with apolar solvents; b) recovering the hydrocinnamic aldehyde of Formula I in enantiopure or enantiomerically enriched form from the crystallized hemiacetal of Formula III and the aldehyde of opposite configuration in enantiopure or enantiomerically enriched form from the hemiacetal crystallization mother liquors. The invention also concerns a process for preparing the alcohol of Formula Il to be introduced into step a).
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Page/Page column 35-36
(2010/12/17)
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- Rhodium-catalyzed one-pot hydroformylation-cyclization of allylbenzene derivatives: Simple and efficient route to 5,6-dihydronaphthalenes
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The one-pot hydroformylation-cyclization of allylbenzene derivatives by the catalyst system Rh(CO)2acac/ultranox626/CO/H2/CH2Cl2 led chemoselectively to 5,6-dihydronaphthalene derivatives 5a-d in good yields. The addition of a catalytic amount of H3PO4 enhanced in situ the cyclization process via the nucleophilic attack on the carbonyl group of the linear aldehyde, and finally the elimination of alcohol. The type of substitution on phenyl group of the allylbenzene is of great importance in enhancing the cyclization process.
- Alhaffar, Mouheddin,Suleiman, Rami,Ali, Bassam El
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experimental part
p. 778 - 782
(2010/07/06)
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- 2-METHYL-3-(3,4-METHYLENEDIOXYPHENYL)PROPANAL, AND METHOD FOR PRODUCTION THEREOF
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Disclosed are: (1) a method for producing 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, which comprises the step of providing a reaction mixture containing 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)-1-propene by a process for reacting 1,2-methylenedioxybenzene with 2-methyl-3,3-diacetoxypropene or a process for reacting 1,2-methylenedioxybenzene, methacrolein and acetic anhydride with one another; subjecting the reaction mixture to hydrolysis or transesterification with an alcohol to provide a reaction mixture containing 2-methyl-3-(3,4-methylenedioxyphenyl)propanal; and purifying by distilling the reaction mixture, wherein a high boiling point compound contained in the reaction mixture is removed by a specific procedure; and (2) 2-methyl-3-(3,4-methylenedioxyphenyl)-propanal produced by the method, which has an acetic acid content of a less than 40 ppm, is useful as a perfume, and has a high purity.
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Page/Page column 15
(2009/12/05)
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- METHOD OF RETAINING THE QUALITY OF 2-METHYL-3-(3,4-METHYLENEDIOXYPHENYL)PROPANAL AND PROCESS FOR PRODUCING THE SAME
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The present invention relates to [1] a method for keeping a quality of 2-methyl-3-(3,4-methylenedioxyphenyl)propanal useful as a perfume, which comprises incorporating from 50 to 3000 ppm of 1-acetyl-3,4-methylenedioxybenzene in the 2-methyl-3-(3,4-methylenedioxyphenyl)propanal; [2] a process for producing 2-methyl-3-(3,4-methylenedioxyphenyl)propanal having a content range from 50 to 3000 ppm of 1-acetyl-3,4-methylenedioxybenzene; and [3] 2-methyl-3-(3,4-methylenedioxyphenyl)propanal having a content range from 50 to 3000 ppm of of 1-acetyl-3,4-methylenedioxybenzene.
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Page/Page column 7; 13
(2009/12/05)
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- PROCESS FOR THE PREPARATION OF 3-(3,4-METHYLENEDIOXYPHENYL)-2-METHYLPROPANAL
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Process for the preparation of 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (I) comprising the following steps: a) reacting 5-propanoyl-1,3- benzodioxol (III) with the Vilsmeier reagent at temperatures ranging between 0° and 40°C and subsequently treating of the reaction mixture with a base in aprotic apolar solvent to obtain the unsaturated chloroaldehyde of formula (IV); b) reacting the unsaturated chloroaldehyde of formula (IV), obtained in the previous step, with hydrogen in the presence of a supported heterogeneous catalyst containing a metal chosen amongst Pd, Pt, Rh, Ru in the presence of an organic base or of a mixture of an organic and inorganic base.
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Page/Page column 9
(2010/02/14)
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- Oxidative coupling of benzenes with α,β-unsaturated aldehydes by the Pd(OAc)2/molybdovanadophosphoric acid/O2 system
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The oxidative coupling reaction of benzene with an α,β- unsaturated aldehyde was examined by the combined catalytic system of Pd(OAc)2 with molybdovanadophosphoric acid (HPMoV) under atmospheric dioxygen. Thus, the reaction of benzene with acrolein under dioxygen (1 atm) by the use of catalytic amounts of Pd(OAc)2 and H4PMo 11VO40·26H2O in the presence of dibenzoylmethane as a ligand in propionic acid at 90 °C for 1.5 h afforded cinnamaldehyde in 59% yield and β-phenylcinnamaldehyde in 5% yield. This catalytic system was extended to the direct oxidative coupling through the C-H bond activation of various arenes with acrolein and methacrolein.
- Yamada, Tomoyuki,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 5471 - 5474
(2008/04/18)
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- Functional fragrance precursor
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The present invention relates to a class of fragrance precursor compounds comprising one or more of the compounds derived from the reaction of X—OH and an aldehyde or ketone, said fragrance precursor compounds being of the formula X—O—C(R) (R*) (OR**) wherein R is a C6-24 alkyl group, a C6-24 aralkyl group or a C6-24 alkaryl group; R* is H or a C6-24 alkyl group, a C6-24 aralkyl group or a C6-24 alkaryl group; R** is H or X; X—O representing a moiety derived from X—OH, and wherein X—OH is a compound selected from the group consisting of surfactants, fabric softeners, softener precursor ester amines, softener precursor amido amines, hair conditioners, skin conditions, saccharides and polymers. In a second aspect it relates to a method of preparing such precusors. Further the invention relates to compositions, comprising the precursor of the invention.
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