- A high-yield, liquid-phase approach for the partial oxidation of methane to methanol using SO3 as the oxidant
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A direct approach for producing methanol from methane in a three-step, liquid phase process is reported. In the first step, methane is reacted with SO3 to form methanesulfonic acid (MSA) at 75°C using a free-radical initiator and MSA as the solvent. Urea-H2O2 in combination with RhCl3 is found to be the most effective initiator (57% conversion of SO3; 7.2% conversion of CH4). MSA is then oxidized by SO3 at 160°C in a second step to produce a mixture containing methyl bisulfate and some methyl methanesulfonate (87% conversion of MSA). In the third step, the mixture of methyl bisulfate and methyl methanesulfonate is hydrolyzed in the presence of an organic solvent, to produce an organic phase containing methanol and an aqueous phase containing sulfuric acid and some MSA (63% conversion of methyl bisulfate; 72% conversion of methyl methanesulfonate). Overall, 58% of the MSA (of which 23% is derived from methane) is converted to methanol.
- Mukhopadhyay, Sudip,Zerella, Mark,Bell, Alexis T.
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Read Online
- METHOD FOR THE PRODUCTION OF ALKANE SULFONIC ACID AT NON-SUPERACIDIC CONDITIONS
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The present invention refers to a method for the production of alkane sulfonic acid, in which SO and an alkane are contacted with each other in the presence of a solvent, said solvent does not constitute a superacid and the combination of said solvent with one or more of the reactants also does not give rise to a superacid.
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Page/Page column 12
(2020/10/09)
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- METHOD FOR THE PRODUCTION OF ALKANE SULFONIC ACID AT SUPERACIDIC CONDITIONS
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The present invention refers to a method for the production of alkane sulfonic acid, in which SO3 and an alkane are contacted with each other in the presence of a solvent, said solvent does constitute a superacid and the combination of said solvent with one or more of the reactants also gives rise to a superacid.
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Page/Page column 12
(2020/10/09)
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- Mechanism and processing parameters affecting the formation of methyl methanesulfonate from methanol and methanesulfonic acid: an illustrative example for sulfonate ester impurity formation
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Sulfonate salts offer useful modification of physicochemical properties of active pharmaceutical ingredients (APIs) containing basic groups, but there are regulatory concerns over the presence of sulfonate esters as potential genotoxic impurities (PGIs).
- Delaney, Ed,Jacq, Karine,Sandra, Pat,David, Frank,Taylor-Worth, Karen,Lipczynski, Andrew,Van, Reif,Elder, David P.,Facchine, Kevin L.,Golec, Simon,Oestrich, Rolf Schulte,Teasdale, Andrew,Eyley, Stephen C.
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supporting information; experimental part
p. 429 - 433
(2010/04/22)
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- A highly active catalyst supported molecular sieves-NaHCO3 mixture for the selective and advantageous N-monoalkylation of amines
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Amines are mono-N-alkylated by alkylmesylates in the presence of catalyst supported molecular sieves-NaHCO3 mixture in a regioselective, chemoselective and non-toxic process. Observed chemoselectivity is supported by 'DFT'.
- Das, Asish R.,Medda, Arunima,Singha, Raghunath,Guchhait, Nikhil
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experimental part
p. 841 - 848
(2010/06/01)
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- DIRECT METHOD AND REAGENT KITS FOR FATTY ACID ESTER SYNTHESIS
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Provided are efficient, cost-effective and water tolerant methods (e.g., single-vial methods) for preparing fatty acid esters from organic matter, comprising: obtaining organic matter comprising at least one fat substituent, contacting the organic matter in a reaction mixture with a basic solution under conditions suitable to provide for hydrolytic release of monomeric fatty acids from the at least one fat substituent to provide a base-treated reaction mixture, and esterifying the monomeric fatty acids of the base-treated reaction mixture by acidification of the reaction mixture and treating in the presence of an organic alcohol to provide fatty acid esters. The methods optionally further comprise, prior to esterifying, neutralizing the base-treated reaction mixture to provide for neutralized fatty acids, separating the neutralized fatty acids from the neutralized reaction mixture, and dissolving the separated fatty acids in the esterification reaction mixture. Also provided are related methods and kits for fat analysis.
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Page/Page column 18; 23; 30
(2008/12/07)
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- PREPARATION AND UTILITY OF SUBSTITUTED INDOLES
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Disclosed herein are substituted indoles of Formula I, processes of preparation there of, pharmaceutical compositions thereof, and methods of their use there of.
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Page/Page column 34
(2008/06/13)
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- Manufacture of higher hydrocarbons from methane, via methanesulfonic acid, sulfene, and other pathways
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Hydrocarbon liquids and olefins can be made from methane with greater efficiency than previously available, by converting methane into methanesulfonic acid (MSA), then converting the MSA into a reactive anhydride called sulfene, H2C═SO2. Sulfene will exothermically form ethylene, an olefin. It also can insert methylene groups (—CH2—) into hydrocarbon liquids, to make heavier and more valuable liquids. Other options are disclosed for improved methods of making MSA (such as by using di(methyl-sulfonyl) peroxide as a radical initiator), for converting MSA into products such as dimethyl ether (DME), and for using DME as a “peak shaving” gas that can be injected into natural gas supply pipelines with no disruptions to end-use burners.
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Page/Page column 25
(2008/06/13)
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- Diaminopyrimidine derivatives as growth hormone secrectgogue receptor (GHS-R) antagonists
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The present invention is related to compounds of formula (I), or a therapeutically suitable salt or prodrug thereof, the preparation of the compounds, compositions containing the compounds and the use of the compounds in the prevention or treatment of disorders regulated by the action of ghrelin receptor, including Prader-Willi syndrome, eating disorder, weight gain, weight-loss maintainance following diet and exercise, obesity, and disorders associated with obesity such as noninsulin dependent diabetes mellitus.
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Page/Page column 48
(2010/02/13)
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- A General and Expeditious One-Pot Synthesis of Sulfoxides in High Optical Purity from Norephedrine-Derived Sulfamidites
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A general and simple procedure for preparing any kind of enantiomerically enriched sulfoxide starting from norephedrine-derived N-benzyloxycarbonylsulfamidite 3a is reported. After one-pot reaction of 3a with RMgX, HBF4, and R'MgX, a variety of sulfoxides 6 are obtained in ee usually higher than 93% and isolated yields ranging between 50 and 78%. The obtained configuration is tunable by simply electing the order of the addition of the reagents.
- Ruano, Jose L. Garcia,Alemparte, Carlos,Aranda, M. Teresa,Zarzuelo, Maria M.
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- Method for producing alkanesulfonic acids
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A process for preparing alkanesulfonic acids from dialkyl sulfites comprises the following steps: rearrangement of dialkyl sulfite in the presence of a suitable catalyst to form the corresponding alkyl alkanesulfonate and hydrolysis of the resulting alkyl alkanesulfonate to give the corresponding alkanesulfonic acid.
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- Ester compounds
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An ester compound represented by the formula: wherein R is a hydrogen atom, a C1-C3 alkyl group unsubstituted or substituted with one or more halogen atoms, an allyl group unsubstituted or substituted with one or more halogen atoms, or a propargyl group unsubstituted or substituted with one or more halogen atoms; and X is a hydrogen atom, a halogen atom, a C1-C3 alkyl group unsubstituted or substituted with one or more halogen atoms, a C2-C3 alkenyl group unsubstituted or substituted with one or more halogen atoms, a C2-C3 alkynyl group unsubstituted or substituted with one or more halogen atoms, a C1-C3 alkoxy group unsubstituted or substituted with one or more halogen atoms, a C1-C3 alkylthio group unsubstituted or substituted with one or more halogen atoms, or a C1-C3 alkoxymethyl group containing a C1-C3 alkoxy group unsubstituted or substituted with one or more halogen atoms, has an excellent pest-controlling effect.
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- Unsensitized photooxidation of sulfur compounds with molecular oxygen in solution
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The short wavelength irradiation of aliphatic disulfides, sulfides and of n-butanethiol in alcohols or aqueous acetonitrile in the presence of oxygen was investigated: the corresponding sulfonic acids are produced in good yields for short alkyl chain compounds, together with smaller amounts of sulfuric and carboxylic acids. In acetonitrile, the influence of added water on the reaction course is evidenced: increased reaction rate and acid yields, control of sulfuric acid formation. Intermediates such as sulfinic acid and thiosulfonate were detected and their rates of formation were monitored. The reaction appears to involve thiyl radicals giving rise to sulfonyl radicals in the presence of oxygen. A first tentative hypothesis concerning the mechanism is advanced.
- Robert-Banchereau, Evelyne,Lacombe, Sylvie,Ollivier, Jean
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p. 2087 - 2102
(2007/10/03)
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- Anchimeric Assistance of the CO2CH3 Substituent in the Elimination Kinetics of 3-(Methoxycarbonyl)propyl Methanesulfonate in the Gas Phase
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The elimination kinetics of 3-(methoxycarbonyl)propyl methanesulfonate have been determined in a static system over the temperature range of 289.3-329.8 deg C and pressure range of 43-111 torr.The reaction, in vessels seasoned with allyl bromide and in the presence of at least an equal amount of the free radical suppressor toluene, is homogeneous, unimolecular and first-order kinetically.The rate coefficients follow the Arrhenius equation: log k1 = (13.50 +/- 0.47) - (182.2 +/- 5.3) (2.303 RT)-1.A very high extent of lactone formation suggests an unequivocal participation of the carbonyl oxygen of the CO2CH3 group.The partial rates for the parallel elimination towards the formation of butyrolactone and a small amount of methylbut-3-enoate have been estimated, reported, and discussed.The present results provide further evidence of intimate ion pair mechanisms in the gas phase pyrolyses of special types of organic molecules.
- Chuchani, Gabriel,Dominguez, Rosa M.
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p. 1295 - 1298
(2007/10/02)
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- Benzophenone Dicarboxylic Acid Antagonists of Leukotriene B4. 2. Structure-Activity Relationships of the Lipophilic Side Chain
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A series of lipophilic benzophenone dicarboxylic acid derivatives were found to inhibit the binding of the potent chemotoxin leukotriene B4 (LTB4) to its receptor on intact human neutrophils.Activity at the LTB4 receptor was determined by using a 3H>LTB4-binding assay.The structure-activity relationship for the lipophilic side chain was systematically investigated.Compounds with n-alkyl side chains of varying lengths were prepared and tested.Best inhibition of 3H>LTB4 binding was observed with the n-decyl derivative.Analogues with alkyl chains terminated with an aromatic ring showed improved activity.The 6-phenylhexyl side chain was optimal.Substitution on the terminal aromatic ring was also evaluated.Methoxyl, methylsulfinyl, and methyl substituents greatly enhanced the activity of the compound.For a given substituent, the para isomer had the best activity.Thus the nature of the lipophilic side chain can greatly influence the ability of the compounds to inhibit the binding of LTB4 to its receptor on intact human neutrophils.The most active compound from this series, 84 (LY223982), bound to the LTB4 receptor with the affinity approaching that of the agonist.
- Gapinski, D. Mark,Mallett, Barbara E.,Froelich, Larry L.,Jackson, William T.
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p. 2807 - 2813
(2007/10/02)
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- POTENTIAL ANTIHISTAMINE AGENTS: 4-(6,11-DIHYDRODIBENZOTHIEPIN-11-YLIDENE)-1-METHYLTETRAHYDROTHIOPYRANIUM IODIDE AND SIMILAR SULFONIUM SALTS DERIVED FROM RELATED TRICYCLIC SYSTEMS
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Thioxanthone, 10,11-dihydrodibenzocyclohepten-5-one, dibenzothiepin-11(6H)-one, its 2-methyl derivative, and thieno-2-benzothiepin-4(9H)-one were reacted with 4-tetrahydrothiopyranylmagnesium bromide and the obtained tertiary alcohols IVabc, VIc, and XIX were dehydrated to the olefinic sulfides IXabc, Xc, and XXI.Addition of methyl iodide afforded the title compounds XIabc, XIIc, and XXII.The Grignard reactions were accompanied by the 1,6-addition giving the ketones XVI-XVIII as by-products.The reductive properties of tetrahydrothiopyranylmagnesium bromide were most striking in the case of reaction with 2-chlorothioxanthone; the isolation of thioxanthene and thioxanthone showed that nuclear dehalogenation took also place.Reactions of 11-chloro-6,11-dihydrodibenzothiepin and benzhydryl chloride with tetrahydrothiopyran-4-ol gave the sulfides XXV and XXVIII; whereas the latter reacted with methyl iodide under the formation of sulfonium salt XXIX, the former was cleaved and gave 4-hydroxyl-1-methyltetrahydrothiopyranium iodide (XXVI).The sulfonium salts are free of the central effects but their antihistamine activity is rather low.
- Polivka, Zdenek,Holubek, Jiri,Budesinsky, Milos,Matousova, Oluse,Svatek, Emil,et al.
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p. 2758 - 2774
(2007/10/02)
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- Mesylhydroxylamines, VI. Oxidation of N-Mesylhydroxylamines - Vibrational Spectra and Structure of 1,2-Dimesyl-1,2-dimethoxyhydrazine
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The oxidation reactions of mesylhydroxylamines proceed mainly via radicals.Oxidation of CH3SO2N(H)OH gives trimesylhydroxylamine (5) probably via the intermediate CH3SO2NO (4).By oxidizing CH3SO2N(H)OCH3 and C6H5SO2N(H)OCH3, derivatives of the hypothetical dihydroxyhydrazine were formed (7a,b).Thermolysis leads to dinitrogen and methyl sulfonate.Oxidation of (CH3SO2)2NOH (1) also gives 5, via 4, but the isomeric CH3SO2N(H)OSO2CH3 is oxidized to nitrate.According to an X-ray structure analysis, 1,2-dimesyl-1,2-dimethoxyhydrazine (7a) crystallizes in the space group P21/n with pyramidally coordinated nitrogen atoms.The vibrational spectra and the structure were discussed in relation to other mesylated nitrogen compounds.
- Brink, Klaus,Mattes, Rainer
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p. 564 - 573
(2007/10/02)
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- Tricyclic polyazaheterocycles for treating depression or anxiety
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The invention relates to novel polycyclic polyazaheterocycles having psychopharmacological properties, especially antidepressive and anxiolytic activity, corresponding to the formula I STR1 in which R1 and R2 each represents, independently of the other, hydrogen, lower alkyl or hydroxy-lower alkyl, or together represent lower alkylene or ethyleneoxyethylene, ethyleneazaethylene or N-lower alkyl- or N-(2-hydroxy-lower alkyl)-ethyleneazaethylene, R3 represents hydrogen or a lower aliphatic hydrocarbon radical or a saturated lower cycloaliphatic hydrocarbon radical or unsubstituted or substituted phenyl, R4 and R5 represent hydrogen or lower alkyl, and Ar represents an unsubstituted or substituted benzo or pyrido radical, and to acid addition salts of compounds of the general formula I, especially the pharmaceutically acceptable acid addition salts of compounds of the general formula I, to pharmaceutical preparations containing these novel substances and to a method of treating conditions of depression or anxiety by administering them.
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- A NEW METHOD FOR THE ESTERIFICATION OF SULPHONIC ACIDS
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Sulphonic acids can be smoothly converted to their methyl and ethyl esters by reaction with trimethyl and triethyl orthoformate, respectively
- Padmapriya, A. A.,Just, G.,Lewis, N. G.
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p. 1057 - 1062
(2007/10/02)
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- Oxidatively Assisted Nucleophic Substitution of Iodine in Alkyl Iodides by Nucleofugic Anions
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The reaction of alkyl iodides with chlorine or nitronium tetrafluoroborate in the presence of salts of perchloric or substitued sulfonic acids gave alkyl perchlorates or sulfonates as principal products.Some mechanistic aspects of this new reaction are discussed.
- Zefirow, Nikolai S.,Zhdankin, Victor V.,Makhon'kova, Galina V.,Dan'kov, Yuri V.,Koz'min, Anatoly S.
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p. 1872 - 1876
(2007/10/02)
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- BIOMIMETIC METHYL TRANSFER TO OLEFINS
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Conditions have been found under which trisubstituted olefins can be methylated with diaryl methyl sulfonium salts in 2,6-di-t-butylpyridine.The pattern of methylated compounds formed is similar to that of the enzymatic methylation of Δ24 steroids side chains with S-adenosylmethionine as a methyl donor.
- Julia, M.,Marazano, C.
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p. 3717 - 3724
(2007/10/02)
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- ALKANESULFONYLATION REACTIONS. I. CHARACTERISTICS OF THE ALKANESULFONYLATION OF PHENOL-d1 AND METHANOL-d1 CATALYZED BY TERTIARY AMINES
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The products from alkanesulfonylation of phenol-d1 and methanol-d1 catalyzed by tertiary amines, which occurs in at least three competing directions (nucleophilic and general base catalysis and a sulfene mechanism), were investigated.The degree of realization of the sulfene mechanism was determined from the content of the ester-d1, and its dependence on the structure of the catalysis, the substrate, the reagent, and the nature of the solvent was investigated.It was shown that the fraction of the ester-d1 decreases with decrease in the basicity and steric accessibility of the tertiary amine.Investigation of the effect of the structure of the sulfonyl chloride shows that the fraction of the sulfene mechanism decreases with decrease in the acidity of the α-protons and their steric accessibility.It was shown that the most favorable conditions for realization of the sulfene mechanism are created in benzene.
- Skrypnik, Yu. G.,Bezrodnyi, V. P.
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p. 511 - 515
(2007/10/02)
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- Benz (c) fluoran compounds and recording sheet containing them
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Novel benz[c]fluoran compounds such as 2-phenylamino-8-diethylamino-benz[c]fluoran, 2-(2',4',6'-trimethylphenylamino)-8-diethylamino-benz[c]fluoran and N-[8-diethylaminobenz[c]fluoran-2-yl]-N-[6-diethylaminofluoran-2-yl]amine, which are useful as a coloring material for record material systems such as pressure-sensitive copying paper or heat-sensitive copying paper, wherein colored images formed by an electron-donoracceptor color-forming reaction between coloring material and acidic material.
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- Chromogenic compounds and method for preparation thereof
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Chromogenic compounds for use in pressure sensitive recording sheets represented by the formula: SPC1 Are disclosed, wherein R1 and R2 are independently, hydrogen substituted or unsubstituted lower alkyl, aliphatic acyl, phenyl substituted aliphatic acyl, benzoyl, aralky, phenyl (the benzene nuclei of those substituents may be further substituted by chlorine, bromine, lower alkyl, lower alkoxy or nitro), allyl, allyl substituted by lower alkyl or phenyl, propargyl, or propargyl substituted by lower alkyl or a phenyl; R3 and R4 are independently lower alkyl, benzyl and phenyl (the benzene nuclei or those substiutents may be further substituted by chlorine, bromine, lower alkyl or lower alkoxy), either R1 or R2 being other than hydrogen when R3 and R4 are both ethyl groups.
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