- Method for combined production of 3-methyl-1,5-pentanediol and C1-C6 alcohols
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The invention provides a method for combined production of 3-methyl-1,5-pentanediol and C1-C6 alcohols. The method comprises the following steps: 1) subjecting 3-methyl-3-butene-1-alcohol and C1-C6 acids to an esterification reaction so as to obtain an esterified product containing C1-C6 acids-3-methyl-3-butene-1-alcohol ester; 2) subjecting the esterified product obtained in the step 1) and gas containing CO and H2 to a hydroformylation reaction; and 3) subjecting a reaction product obtained in the step 2) to a hydrogenation reaction so as to obtain the 3-methyl-1,5-pentanediol and the C1-C6alcohols. According to the invention, through a process route of esterification, hydroformylation and hydrogenation in turn, direct hydroformylation of 3-methyl-3-butene-1-alcohol is avoided, so inevitable side reactions generated by a direct hydroformylation reaction is easily avoided; meanwhile, by utilization of the process route provided by the invention, combined production of the C1-C6 alcohols (like ethyl alcohol) can be realized.
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Paragraph 0104; 0105; 0107
(2018/07/30)
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- METHODS OF FORMING DIOL COMPOUNDS
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Methods of forming a C4 to C7 diol compound, the methods including a first step of reacting a C4 to C7 dicarboxylic acid with hydrogen (H2) gas on a first heterogeneous catalyst at a first temperature and a first pressure to form a C4 to C7 lactone; and a subsequent step of reacting the lactone with hydrogen (H2) gas on a second heterogeneous catalyst at a second temperature and a second pressure, wherein the second temperature is lower than the first temperature. Also disclosed are methods of forming a solvent, the methods including reacting a C4 to C7 dicarboxylic acid with hydrogen (H2) gas on a first heterogeneous catalyst at a first temperature and a first pressure to form a solvent. Further disclosed herein are methods that include reacting mevalonolactone with hydrogen (H2) gas on a second heterogeneous catalyst at a second temperature and a second pressure to form a diol compound.
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- Branched Diol Monomers from the Sequential Hydrogenation of Renewable Carboxylic Acids
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A prominent challenge in replacing petrochemical polymers with bioderived alternatives is the efficient transformation of biomass into useful monomers. In this work, we demonstrate a practical process for the synthesis of multifunctional alcohols from five- and six-carbon acids using heterogeneous catalysts in aqueous media. Design of this process was guided by thermodynamic calculations, which indicate the need for two sequential high-pressure hydrogenations: one, reduction of the acid to a lactone at high temperature; two, further reduction of the lactone to the corresponding diol or triol at low temperature. For example, the conversion of mesaconic acid into (α or β)-methyl-γ-butyrolactone was achieved with 95 % selectivity at a turnover frequency of 1.2 min?1 over Pd/C at 240 °C. Subsequent conversion of (α or β)-methyl-γ-butyrolactone into 2-methyl-1,4-butanediol was achieved with a yield of 80 % with Ru/C at 100 °C. This process is an efficient method for the production of lactones, diols, and triols, all valuable monomers for the synthesis of bioderived branched polyesters.
- Spanjers, Charles S.,Schneiderman, Deborah K.,Wang, Jay Z.,Wang, Jingyu,Hillmyer, Marc A.,Zhang, Kechun,Dauenhauer, Paul J.
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p. 3031 - 3035
(2016/10/11)
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- POLYMERS PREPARED FROM MEVALONOLACTONE AND DERIVATIVES
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Described herein polymer precursor compounds (aka polymer building blocks) of derived from biobased compounds, and specifically biobased mevalonolactone and its related derivatives. Through oxidation these biobased precursors can be reacted to yield building blocks for (unsaturated-) polyesters, polyester polyols and polyamides, as well as precursors for glycidyl esters and omega-alkenyl esters. Through reduction, these biobased precursors can be reacted to yield building blocks for (unsaturated-) polyesters, polyester polyols, polycarbonates, as well as precursors for glycidyl ethers and omega-alkenyl ethers. Through nucleophilic ring opening and/or amidation, these biobased precursors can be reacted to yield building blocks for polyester polyols, chain-extender for polyurethanes, or polyester-amides.
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Page/Page column 52
(2016/06/06)
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- PROCESS FOR PRODUCING POLYHYDRIC ALCOHOL
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A process for producing a polyhydric alcohol includes a step (I) of hydrogenating hemiacetal having a specific structure to obtain a reaction solution (I), and a step (II) of adding water to the reaction solution (I) obtained in the step (I) and further conducting hydrogenation.
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Paragraph 0062; 0063
(2016/05/24)
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- Process for producing polyhydric alcohol
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A process for producing a polyhydric alcohol which comprises a step (I) in which a hemiacetal having a specific structure is hydrogenated to obtain a liquid reaction mixture (I) and a step (II) in which water is added to the liquid reaction mixture (I) obtained in the step (I) to further conduct hydrogenation.
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Paragraph 0101; 0102; 0103
(2016/10/08)
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- POLYMERS PREPARED FROM MEVALONOLACTONE AND DERIVATIVES
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Described herein polymer precursor compounds (aka polymer building blocks) of derived from biobased compounds, and specifically biobased mevalonolactone and its related derivatives. Through oxidation these biobased precursors can be reacted to yield building blocks for (unsaturated-) polyesters, polyester polyols and polyamides, as well as precursors for glycidyl esters and omega-alkenyl esters. Through reduction, these biobased precursors can be reacted to yield building blocks for (unsaturated-) polyesters, polyester polyols, polycarbonates, as well as precursors for glycidyl ethers and omega-alkenyl ethers. Through nucleophilic ring opening and/or amidation, these biobased precursors can be reacted to yield building blocks for polyester polyols, chain-extender for polyurethanes, or polyester-amides.
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- METHOD FOR PRODUCTION OF 3-METHYL-1,5-PENTANEDIOL
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Provided is a method for producing 3-methyl-1,5-pentanediol by hydrogenating 2-hydroxy-4-methyltetrahydropyran in the presence of a hydrogenation catalyst, characterized in that the hydrogenation is further carried out in the presence of a basic compound. By this method, in producing MPD by hydrogenation of MHP, high-purity MPD can be produced by effectively suppressing generation of by-products such as MPAE and MVL even when a known hydrogenation catalyst is used.
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Page/Page column 5-6
(2009/02/10)
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- METHOD FOR PRODUCING 3-METHYL-1,5-PENTANEDIOL
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Provided is a method for producing 3-methyl-1,5-pentanediol by hydrogenating 2-hydroxy-4-methyltetrahydropyran in the presence of a hydrogenation catalyst, characterized in that the hydrogenation is further carried out in the presence of a basic compound. By this method, in producing MPD by hydrogenation of MHP, high-purity MPD can be produced by effectively suppressing generation of by-products such as MPAE and MVL even when a known hydrogenation catalyst is used.
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Page/Page column 3
(2009/04/25)
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- Design, synthesis, and antipicornavirus activity of 1-[5-(4-arylphenoxy) alkyl]-3-pyridin-4-ylimidazolidin-2-one derivatives
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A series of pyridylimidazolidinone derivatives was synthesized and tested in vitro against enterovirus 71 (EV71). On the basis of compound 33 (DBPR103), introduction of a methyl group at the 2- or 3-position of the linker between the imidazolidinone and the biphenyl resulted in markedly improved antiviral activity toward EV71 with IC50 values of 5.0 nM (24b) and 9.3 nM (14a), respectively. Increasing the branched chain to propyl resulted in a progressive decrease in activity, while inserting different heteroatoms entirely rendered the compound only weakly active. The introduction of a bulky group (cyclohexyl, phenyl, or benzyl) led to loss of activity against EV71. The 4-chlorophenyl moiety in 14a was replaced with bioisosteric groups such as oxadiazole (28a-d) or tetrazole (32a,b), dramatically improving anti-EV71 activity and selectivity indices. Compounds 14a, 24b, 28b, 28d, and 32a exhibited a strong activity against lethal EV71, and no apparent cellular toxicity was observed. Three of the more potent imidazolidinone compounds, 14a, 28b, and 32b, were subjected to a large group of picornaviruses to determine their spectrum of antiviral activity.
- Chang, Chih-Shiang,Lin, Ying-Ting,Shih, Shin-Ru,Lee, Chung-Chi,Lee, Yen-Chun,Tai, Chia-Liang,Tseng, Sung-Nien,Chern, Jyh-Haur
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p. 3522 - 3535
(2007/10/03)
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- Synthesis and antipicornavirus activity of (R)- and (S)-1-[5-(4′- chlorobiphenyl-4-yloxy)-3-methylpentyl]-3-pyridin-4-yl-imidazolidin-2-one
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The new pyridyl imidazolidinone derivative, 1-[5-(4′-chlorobiphenyl- 4-yloxy)-3-methylpentyl]-3-pyridin-4-yl-imidazolidin-2-one (±)-1a, was synthesized and found to have an excellent antiviral activity against EV71 (IC50 = 0.009 μM). Therefore, both the enantiomers, (S)-(+)-1a and (R)-(-)-1a, have been prepared starting from readily available monomethyl (R)-3-methylglutarate (7) as a useful chiral building block and their antiviral activity was evaluated in a plaque reduction assay. Interestingly, we observed that the enantiomer (S)-(+)-1a was 10-fold more active against enterovirus71 (EV71) (IC50 = 0.003 μM) than the corresponding enantiomer (R)-(-)-1a (IC50 = 0.033 μM). Similar results were found against all five strains (1743, 2086, 2231, 4643, and BrCr) of EV71 tested. This demonstrated that the absolute configuration of the chiral carbon atom at the 3-position of the alkyl linker considerably influenced the anti-EV71 activity of these pyridyl imidazolidinones.
- Chern, Jyh-Haur,Chang, Chih-Shiang,Tai, Chia-Liang,Lee, Yen-Chun,Lee, Chung-Chi,Kang, Iou-Jiun,Lee, Ching-Yin,Shih, Shin-Ru
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p. 4206 - 4211
(2007/10/03)
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- Synthesis and biological characterization of (Z)-9-heptadecenoic and (Z)-6-methyl-9-heptadecenoic acids: Fatty acids with antibiotic activity produced by Pseudozyma flocculosa
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Difficulties in isolating and purifying antibiotic fatty acids from culture filtrates of Pseudozyma flocculosa, a biocontrol agent against powdery mildew, have been limiting factors in studying the properties and understanding the mode of action of the biocontrol agent. We report a new protocol for synthesizing (Z)-9-heptadecenoic and for the first time synthesis of (Z)-6-methyl-9-heptadecenoic acids, two antibiotic fatty acids produced by P. flocculosa. This allowed reproducible and quantifiable means of assaying biological activity of the molecules. In these bioassays, both molecules exhibited antifungal activity corresponding to their expected potency. These new developments should facilitate further studies aimed at deciphering the ecological properties of P. flocculosa.
- Avis,Boulanger,Belanger
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p. 987 - 1000
(2007/10/03)
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- SIGMATROPIC RING EXPANSION OF CYCLIC THIONOCARBONATES. 9. TOTAL SYNTHESIS OF (+/-)-YELLOW SCALE PHEROMONE VIA 10-MEMBERED THIOLCARBONATE
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(+/-)-Yellow scale pheromone 1 has been synthesized via the route illustrated in Scheme 1.The sigmatropic ring expansion of 8-membered thionocarbonate 4 exclusively produced the (Z)-10-membered thiolcarbonate 3, which was transformed via three steps to the intermediate 2 with all the necessary carbon atoms for the pheromone.Reductive removal of the SCO mioety in 2 followed by acetylation gave 1.
- Harusawa, Shinya,Takemura, Shigetaka,Osaki, Hirotaka,Yoneda, Ryuji,Kurihara, Takushi
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p. 7657 - 7666
(2007/10/02)
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- Oxidation of putrescine and cadaverine derivatives by diamine oxidases
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A range of putrescine and cadaverine derivatives has been synthesized and assayed as substrates for the diamine oxidases from pea seedlings and pig kidney. KM and Vmax data are reported, mainly for the pea enzyme. N-Alkylputrescines and C-alkylcadaverines are generally poorer substrates than the parent compounds with up to 4500-fold reduction in Vmax. There is significantly less variation in KM values, indicating that the binding site of the pea enzyme is relatively non-specific and that enzymic specificity lies at the catalytic stage. This suggests that poor substrates might act as convenient, short-lived inhibitors of diamine oxidases.
- Equi, Angela M.,Brown, Alison M.,Cooper, Alan,Her, Surjit K.,Watson, Allan B.,Robins, David J.
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p. 507 - 518
(2007/10/02)
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- Selective Substitution of Aliphatic Remote Tetriary Hydrogens by Fluorine
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Substitution of saturated hydrogens is a very desirable but difficult task.Elemental fluorine under suitable conditions, including a polar solvent and low temperatures, acts as an electrophile strong enough to react with saturated tetriary CH bonds of various aliphatic compounds.The regioselectivity and the readiness of the hydrogen substitution by fluorine are functions of the p-orbital contribution to the bond, in agreement with the electrophilic nature of the reaction.Apart from branched paraffins, oxygen- as well as nitrogen-containing aliphatic molecules can participate in the reaction, and various protecting groups and their effectiveness were examined.The role of the electron-withdrawing group on the selectivity was also evaluated.
- Rozen, Shlomo,Gal, Chava
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p. 4928 - 4933
(2007/10/02)
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- Hydroformylation of 3-methyl-3-buten-1-ol and analogs thereof and use of such hydroformylation products
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There is disclosed a method of hydroformylating 3-methyl-3-buten-1-ol and analogs thereof with carbon monoxide and hydrogen in the presence of a rhodium compound free from modification by a ligand containing an element belonging to the group V of the periodic table as well as a method of producing 3-methylpentane-1,5-diol and β-methyl-δ-valerolactone using such hydroformylation product.
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