- INDOLE DERIVATIVES AS ALPHA-1 -ANTITRYPSIN MODULATORS FOR TREATING ALPHA-1 -ANTITRYPSIN DEFICIENCY (AATD)
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Indole derivatives as alpha-l-antitrypsin modulators for treating alpha-l-antitrypsin deficiency (AATD).
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Paragraph 00234; 00316; 00778
(2021/10/11)
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- Method for preparing 2-methyl-1, 3-propylene glycol from isobutene
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The invention discloses a method for preparing 2-methyl-1, 3-propylene glycol from isobutene. The method comprises the following steps: mixing isobutene with acetic acid and oxygen, and carrying out an oxyacetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylene propane-1, 3-diacetoxy, namely a compound (C); carrying out transesterification on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D); and carrying out hydrogenation reaction on the compound (D) to obtain the 2-methyl-1,3-propylene glycol. According to the method, the 2-methyl-1, 3-propylene glycol can be generated with high selectivity, and the whole process is high in atom utilization rate, environmentally friendly and suitable for large-scale industrial application.
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Paragraph 0054-0055; 0061; 0063; 0079; 0082-0083; 0086-0087;
(2021/02/10)
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- Manganese(I)-Catalyzed β-Methylation of Alcohols Using Methanol as C1 Source
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Highly selective β-methylation of alcohols was achieved using an earth-abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)2Br[HN(C2H4PiPr2)2]] 1 ([HN(C2H4PiPr2)2]=MACHO-iPr). The reaction requires only low loadings of 1 (0.5 mol %), methanolate as base and MeOH as methylation reagent as well as solvent. Various alcohols were β-methylated with very good selectivity (>99 %) and excellent yield (up to 94 %). Biomass derived aliphatic alcohols and diols were also selectively methylated on the β-position, opening a pathway to “biohybrid” molecules constructed entirely from non-fossil carbon. Mechanistic studies indicate that the reaction proceeds through a borrowing hydrogen pathway involving metal–ligand cooperation at the Mn-pincer complex. This transformation provides a convenient, economical, and environmentally benign pathway for the selective C?C bond formation with potential applications for the preparation of advanced biofuels, fine chemicals, and biologically active molecules.
- Kaithal, Akash,van Bonn, Pit,H?lscher, Markus,Leitner, Walter
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supporting information
p. 215 - 220
(2019/12/03)
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- Hydroformylation process
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A catalyst, useful for the hydroformylation of allyl alcohol, is described. The catalyst comprises a rhodium complex and a 6-bis(3,5-dialkylphenyl)phosphino-N-pivaloyl-2-aminopyridine or a 3-bis(3,5-dialkylphenyl)phosphino-2H-isoquinolin-1-one. The invention also includes a process for the production of 4-hydroxybutyraldehyde comprising reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and the catalyst. The process gives a high ratio of the linear product 4-hydroxybutyraldehyde to the branched co-product 3-hydroxy-2-methylpropionaldehyde.
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Page/Page column 7-8
(2010/09/09)
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- Direct hydrocarbonylation process
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A direct hydrocarbonylation process for the production of 1,4-butanediol is described. The process comprises reacting allyl alcohol with carbon monoxide and hydrogen in an alcohol solvent in the presence of a catalyst system comprising a rhodium complex, a trialkyl phosphine, and a diphosphine. The process gives a high yield of 1,4-butanediol in a one-step reaction.
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Page/Page column 4-5
(2010/02/17)
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- Pheromones and analogs from Neozeleboria wasps and the orchids that seduce them: a versatile synthesis of 2,5-dialkylated 1,3-cyclohexanediones
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Chiloglottone, a wasp pheromone and attractant of sexually deceptive Chiloglottis orchids, and several structural analogs were synthesized. The synthetic approach is facile, high yielding and versatile, enabling rapid divergence to generate dialkylated analogs of chiloglottone. The key transformation was an organocadmium-mediated desymmetrization of glutaric anhydride derivatives. This library of synthetic 2,5-dialkylated 1,3-cyclohexanediones may assist in future identification of natural products in further species.
- Poldy, Jacqueline,Peakall, Rod,Barrow, Russell A.
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p. 2446 - 2449
(2008/09/20)
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- 4-((PHENOXYALKYL)THIO)-PHENOXYACETIC ACIDS AND ANALOGS
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The invention features 4-((phenoxyalkyl)thio)-phenoxyacetic acids and analogs, compositions containing them, and methods of using them as PPAR delta modulators to treat or inhibit the progression of, for example, dyslipidemia.
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Page/Page column 47-48
(2010/02/11)
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- PROCESS FOR THE HYDROFORMYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
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The present invention provides a process for the hydroformylation of ethylenically unsaturated compounds, which process comprises reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of a catalyst system and a solvent, the catalyst system obtainable by combining: a) a metal of Group VIII or a compound thereof; and b) a bidentate phosphine, the process characterised in that a chlorine moiety is present in at least one of the said Group VIII metal compound or said solvent.
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- Ring-opening of 2,3-epoxy-1-propanol with R3Al: Unprecedented regiochemical switching simply achieved by changing alkyl substituents of aluminium reagent
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Several control experiments were designed to optimize the reaction of 2,3-epoxy-1-propanol with R3Al (R = Me, Et or iBu) and to probe for the nature of aluminium-bound alkyl groups that influence the reactivity and selectivity. The reported studies revealed that the Et 3Al mediated reaction leads to the C-2 product in contrast to the well-known C-3 substitution promoted by Me3Al.
- Lewiński, Janusz,Horeglad, Pawe?,Tratkiewicz, Ewa,Justyniak, Iwona,Ochal, Zbigniew
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p. 3697 - 3699
(2007/10/03)
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- DERMATOLOGICAL COMPOSITIONS AND METHODS
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Disclosed are methods and compositions for regulating the melanin content of mammalian melanocytes; regulating pigmentation in mammalian skin, hair, wool or fur; treating or preventing various skin and proliferative disorders; by administration of various compounds, including alcohols, diols and/or triols and their analogues.
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- Chemo-enzymatic synthesis of the C15-C23 unit of Leptomycin B
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The asymmetric synthesis of the C15-C23 unit of Leptomycin B (LMB) is described. All four stereocenters of the C15-C23 unit were prepared from one building block exhibiting only one stereocenter. This building block was synthesized via either an enzymatic transformation or starting from a chiral reagent.
- Scheck, Michael,Waldmann, Herbert
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p. 571 - 576
(2007/10/03)
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- Treatment of diseases mediated by the nitric oxide/cGMP/protein kinase G pathway
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Disclosed are methods and compositions for stimulating cellular nitric oxide (NO) synthesis, cyclic guanosine monophosphate levels (cGMP), and protein kinase G (PKG) activity for purposes of treating diseases mediated by deficiencies in the NO/cGMP/PKG signal transduction pathway, by administration of various compounds including alcohols, diols and/or triols and their analogues.
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- Tethered α-boryl radical cyclizations of haloalkyl boronates
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Boroalkyl radicals readily cyclize onto alkenyl and alkynyl traps tethered via a C-B-O linkage. Oxidative cleavage of the C-B bond of the temporary connection following cyclization affords 1,3-diols in good yields.
- Batey, Robert A.,Smil, David V.
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p. 9183 - 9187
(2007/10/03)
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- Studies on Mercury(II)-Mediated Opening of Bi- and Tercyclopropane Arrays
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The first examples of the mercury(II)-mediated ring opening of bicyclopropane and tercyclopropane arrays have been investigated. The presence of an adjacent cyclopropyl group dramatically increased the rate of the mercury-mediated opening of the first cyclopropane in a cyclopropane array. In contrast to the mercury-mediated ring opening of monocyclopropanes which usually undergo a concerted ring-opening mechanism, electrophilic openings of cyclopropane arrays occurred through a stabilized, free carbocation. Excellent regio- and stereoselectivities were observed in the mercury- mediated intramolecular openings of the second cyclopropanes in the cyclopropane arrays, giving rise to the formation of enantiomerically pure, highly substituted tetrahydrofurans.
- Barrett, Anthony G. M.,Tam, William
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p. 4653 - 4664
(2007/10/03)
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- Hydrocarbonylation of prop-2-en-1-ol to butane-1,4-diol and 2-methylpropan-1-ol catalysed by rhodium triethylphosphine complexes
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The hydrocarbonylation of prop-2-ene-1-ol catalysed by [Rh2(O2CMe)4]-PEt3, which gives [RhH(CO)(PEt3)2] as the active species, has been found to produce predominantly butane-1,4-diol and 2-methylpropan-1-ol with small amounts of 2-methylpropane-1,3-diol and propan-1-ol. Neither 2-methylprop-2-enal nor 2-methylprop-2-en-1-ol are intermediates in the production of 2-methylpropan-1-ol. By carrying out the reaction under a variety of reaction conditions and by using deuterium-labelling studies it was possible to formulate a mechanism for the production of 2-methylpropan-1-ol which involves formation of the vinyl alcohol, 2-methylprop-1-en-1-ol, as the primary product followed by tautomerism and hydrogenation, provided that at least two PEt3 groups are co-ordinated to the rhodium. A dehydration is proposed to occur during the catalytic cycle from a cationic hydroxycarbene intermediate. Using propenyl ethers as substrates similar products are obtained presumably via loss of alcohol rather than dehydration. If less than two PEt3 groups are co-ordinated to rhodium the major branched-chain product from prop-2-en-1-ol is 2-methylpropane-1,3-diol. This is interpreted as indicating that protonation of the acyl intermediate and dehydration of the hydroxycarbene do not occur because of the lower electron density on the acyl O atom.
- Simpson, Michael C.,Currie, Alan W. S.,Andersen, Jo-Ann M.,Cole-Hamilton, David J.,Green, Michael J.
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p. 1793 - 1800
(2007/10/03)
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- Separation of methylene chloride from tetrahydrofuran by extractive distillation
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Methylene chloride is difficult to separate from tetrahydrofuran by conventional distillation or rectification because of the proximity of their vapor pressures. Methylene chloride can be readily separated from tetrahydrofuran by extractive distillation. Effective agents are 1-pentanol, 1,2-butanediol and 3-nitrotoluene.
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- General Synthesis of Methyl- and Dimethyl-cyclobutanes from Simple 1,3-Diols by Phase Transfer Catalysis
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A general method is described for the preparation of methyl- and dimethyl-cyclobutanes from simple 1,3-diols.The key steps of the procedure are a phase transfer catalysed ring closure and the transformation of a carboxyl group to a methyl group.Phase transfer catalysis provides good yields in the synthesis of the cyclobutane skeleton.
- Toeroek, Bela,Molnar, Arpad
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p. 801 - 804
(2007/10/02)
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- Process for producing a deprotected alkoxylated polyol
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An improved process for the hydrolysis and purification of an alkoxylated polyol containing a ketal protective functionality, and which may be employed to prepare reduced calorie esterified alkoxylated polyol fat mimetics useful in cooking and in food compositions, comprises contacting an aqueous mixture of the protected alkoxylated polyol with an acid to hydrolyse and thus deprotect the alkoxylated polyol,adding a base to neutralise the acid and cause the mixture to form a first phase containing the deprotected alkoxylated polyol and a second phase containing predominantly water, and separating the phases. The protected alkoxylated polyol may be formed by alkoxylating a protected polyol. The deprotected alkoxylated polyol may subsequently be esterified.
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- Enantioselective transesterification of 2-methyl-1,3-propanediol derivatives catalyzed by Pseudomonas fluorescens lipase in an organic solvent
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The irreversible transesterification of racemic 2-methyl-1,3-propanediol derivatives, the monoethers 3a, 3b, 5a, and the monobenzoate 5b, with vinyl acetate catalyzed by Pseudomonas fluorescens lipase in chloroform affords enantiomerically pure chiral synthons.
- Grisenti,Ferraboschi,Manzocchi,Santaniello
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p. 3827 - 3834
(2007/10/02)
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- An efficient chemo-enzymatic approach to the enantioselective synthesis of 2-methyl-1,3-propamedical derivatives
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Lipase-catalyzed transesterification of 2-methyl-1,3-propanediol 1 in chloroform affords enantiomerically pure (S)-(-)-acetate 2, from which the (R)-(+)-silyl ethers 4a-b can be efficiently prepared (>98% ee). The (S)-TBDPS derivative 4b could be also efficiently and enantioselectively prepared by the same enzymatic procedure, starting from racemic 5b.
- Santaniello, Enzo,Ferraboschi, Patrizia,Grisenti, Paride
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p. 5657 - 5660
(2007/10/02)
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- Synthesis and Liquid Crystal Properties of Dimethylene Linked Compounds Incorporating the Cyclobutane or Spiroheptane Rings
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The preparation of sixteen dimethylene linked compounds is described heptane ring>, and a comparison is made between the transition temperatures of these compounds and those of the corresponding esters.This comparison once again highlights the fact that the cyclobutane ring should be regarded, in terms of its ability to promote nematic thermal stability, as a "chain stiffener rather than as a ring system.A comparison is also made of the nematic thermal stabilities of the trans-cyclobutane and the spiroheptane systems and of the trans-cyclohexane and the spiroundecane systems.
- Chan, L. K. M.,Gemmell, P. A.,Gray, G. W.,Lacey, D.,Toyne, K. J.
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p. 229 - 246
(2007/10/02)
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- Synthesis and liquid crystal properties of compounds incorporating cyclobutane, spiroheptane and dispirodecane rings
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A number of esters of structure (I) incorporating the cyclobutane, spiroheptane, or dispirodecane rings has been prepared using a diethyl malonate synthesis.Strict comparison of the liquid crystal behaviour amongst the three classes containing a terminal cyano-substituent was not possible because both the cyclobutanes and dispirodecanes are mixtures of cis- and trans-isomers; the spiroheptanes are racemic systems.Using preparative hplc, it was however possible to isolate the pure cis- and trans-isomers of two of the cyano-substituted cyclobutane esters (I; R = alkyl, -X- = --, Y = CN).From the physical data and the results for the corresponding spiroheptane esters, conclusions regarding the effects of these ring systems on liquid crystal behaviour were obtained.The pure cis- and trans-isomers of the cyclobutane ester (I, R = C3H7, -X- = --, Y = CN) have been assessed for the trends in both order parameter and viscosity with temperature; the results support the idea that idea that the trans-cyclobutane ring adopts a more planar conformation at higher temperatures.Keywords: cyclobutane- and related spiro-systems, cis-/trans-isomerism, order parameter, briefringence, viscosity, structure/property relations.
- Chain, L. K. M.,Gemmel, P. A.,Gray, G. W.,Lacey, D.,Toyne, K. J.
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p. 113 - 140
(2007/10/02)
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- Reactions of Methyl Radicals with 3-Methyloxetane, 3,3-Dimethyloxetane and 2,2-Dimethyloxetane
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The reactions of methyl radicals with 3-methyloxetane, 3,3-dimethyloxetane and 2,2-dimethyloxetane have been studied.The overall rates of hydrogen-atom abstraction from these three compounds have been obtained over the temperature range 100-200 deg C by assuming the value of Quinn and coworkers (J.Chem.Soc.Faraday Trans.I, 1976, 72, 1935) for the rate of recombination of methyl radicals.The following rate expressions were found: log10(k4/cm3mol-1s-1)(30x) = 11.69 (+/-0.20)-38.23 (+/-0.84) kJmol-1/2.303RT, log10(k4/cm3mol-1s-1)(3,30x) = 11.72 (+/-0.20)-39.47 (+/-1.0) kJmol-1/2.303RT, log10(k4/cm3mol-1s-1)(2,20x) = 11.99 (+/-0.23)-41.24 (+/-1.13) kJmol-1/2.303RT.From these rate expressions and those obtained previously for three other oxetane molecules, the rate parameters for hydrogen-atom abstraction from five distinct sites in the substituted oxetane molecules have been obtained.
- Duke, Martin G.,Holbrook, Kenneth A.
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p. 3391 - 3398
(2007/10/02)
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- Enantiotopically Selective Oxidation of α,ω-Diols with the Enzyme Systems of Microorganisms
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Gluconobacter were found to be capable of oxidizing prochiral diols such as 2-substituted propane-1,3-diols 1 and 3-substituted pentane-1,5-diols 4 with distinction of pro-R and pro-S sites of the molecules, in that (-)-(R)-α-substituted β-hydroxypropionic acids 2 and (+)-(3S)-3-substituted δ-valerolactones 5 were obtained, respectively.Oxidation of 3-methylpentane-1,3,5-triol 11 afforded unnatural (+)-(S)-mevalonolactone 12.The steric bulkiness of the substituents on the prochiral center and the distance from the hydroxy group greatly affected the rate and the enantioselectivity of the reaction.
- Ohta, Hiromichi,Tetsukawa, Hatsuki,Noto, Naoko
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p. 2400 - 2404
(2007/10/02)
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- 2-Oxo-1,3,2-dioxathianes. I. Preparation of the Alkyl-substituted Derivatives
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2-Oxo-1,3,2-dioxathiane, all methyl- and several other alkyl-substituted 2-oxo-1,3,2-dioxathianes have been synthesized by condensing 1,3-alkanediols and thionyl chloride.The amount of the S==O-axial and S==O-equatorial isomers can be controlled by adding pyridine to the reaction mixture.
- Virtanen, Terttu,Nikander, Hannu
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p. 113 - 116
(2007/10/02)
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- A 13C AND 1H NMR STUDY OF FORMALDEHYDE REACTIONS WITH ACETALDEHYDE AND ACROLEIN. SYNTHESIS OF 2-(HYDROXYMETHYL)-1,3-PROPANEDIOL
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The 13C i 1H NMR spectra of various formaldehyde-acetaldehyde and formaldehyde-acrolein mixtures in buffered aqueous solutions were examined.Reaction intermediates and products were assayed including 3-hydroxypropanal, 3-hydroxy-2-(hydroxymethyl)propanal, pentaerythrose and pentaerythritol.Reaction mixtures were hydrogenated under various conditions to yield mixtures of 1,3-propanediol, pentaerythritol and 2-(hydroxymethyl)-1,3-propanediol.The latter compound was also prepared by an efficient new procedure from 3,3-diethoxy-2-(hydroxymethyl)-1-propanol.
- Nielsen, Arnold T.,Moore, Donald W.,Schuetze, Bryan D.
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p. 1393 - 1403
(2007/10/02)
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- Hydroboration. 57. Hydroboration with 9-Borabicyclononane of Alkenes Containing Representative Functional Groups
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The hydroboration of alkenes containing representative functional groups was examined with 9-borabicyclononane (9-BBN) in order to extend the hydroboration reaction for the preparation of functionally substituted organoboranes.Terminal alkenes containing a remote functional group are hydroborated with a remarkable regioselectivity (>=98percent terminal), producing the corresponding stable organoboranes. 9-BBN hydroborates the allylic derivatives so as to place boron essentially on the terminal carbon atom (>=97percent).The directive effect is further enhanced (>=99percent) in the case of β-methylallyl derivatives.The hydroboration of crotyl derivatives attaches boron predominantly at the 2-position, followed by an elimination-rehydroboration sequence.However, crotyl alcohol can be protected against elimination as the tert-butyl or tetrahydropyranyl ethers.The hydroboration-oxidation of ethyl crotonate involves a series of elimination, hydroboration, and condensation processes.In the vinyl, crotyl, and isobutenyl systems, the mesomeric effect of the substituent favors the placement of boron at the β-position, while the inductive effect favors the α-position, with the former effect predominating in most cases.Acyclic β-substituted organoboranes undergo rapid elimination.Nonpolar solvents and lower reaction temperatures decrease the rate of elimination.However, those derived from cyclic vinyl derivatives are relatively stable under neutral conditions, undergoing facile elimination in the presence of a base.
- Brown, Herbert C.,Chen, Jackson C.
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p. 3978 - 3988
(2007/10/02)
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- Process for preparing 2-methylpropane-1,3-diol
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2-Methylpropane-1,3-diol is prepared by reacting 2-methylenepropane-1,3-diol diacetate with a monohydric, lower aliphatic alcohol in the presence of a base. Thereafter the resulting 2-methylenepropane-1,3 diol is catalytically hydrogenated to form 2-methylpropane-1,3-diol.
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- Process for preparing allylic esters of carboxylic acids
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A process for preparing allylic esters of carboxylic acids which comprises reacting a mixture of a lower alkyl carboxylate ester, water, and the corresponding carboxylic acid and alcohol with an olefin having an allylic carbon-hydrogen bond and oxygen in the presence of an oxidation catalyst.
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