96-48-0Relevant articles and documents
Production of γ-butyrolactone from biomass-derived 1,4-butanediol over novel copper-silica nanocomposite
Hwang, Dong Won,Kashinathan, Palraj,Lee, Jong Min,Lee, Jeong Ho,Lee, U-Hwang,Hwang, Jin-Soo,Hwang, Young Kyu,Chang, Jong-San
, p. 1672 - 1675 (2011)
γ-Butyrolactone was produced highly selectively from biomass-derived 1,4-butanediol by vapor-phase dehydrocyclization over novel copper-silica nanocomposite catalyst. Compared with usual Cu(12)/SiO2, the highly Cu-loaded SiO2 nanocomposite (80 wt%) exhibited high catalyst performance with 98% yield on 400 h stream without significant deactivation even in the absence of H2.
Synthesis and metal binding properties of N-alkylcarboxyspiropyrans
Perry, Alexis,Kousseff, Christina J.
, p. 1542 - 1550 (2017)
Spiropyrans bearing an N-alkylcarboxylate tether are a common structure in dynamic, photoactive materials and serve as colourimetric/fluorimetric cation receptors. In this study, we describe an efficient synthesis of spiropyrans with 2–12 carbon atom alkylcarboxylate substituents, and a systematic analysis of their interactions with metal cations using 1H NMR and UV-visible spectroscopy. All N-alkylcarboxyspiropyrans in this study displayed a strong preference for binding divalent metal cations and a modest increase in M2+ binding affinity correlated with increased alkycarboxylate tether length.
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Nikishin et al.
, (1973)
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Nikishin et al.
, (1971)
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Convergent Cascade Catalyzed by Monooxygenase–Alcohol Dehydrogenase Fusion Applied in Organic Media
Huang, Lei,Aalbers, Friso S.,Tang, Wei,R?llig, Robert,Fraaije, Marco W.,Kara, Selin
, p. 1653 - 1658 (2019)
With the aim of applying redox-neutral cascade reactions in organic media, fusions of a type II flavin-containing monooxygenase (FMO-E) and horse liver alcohol dehydrogenase (HLADH) were designed. The enzyme orientation and expression vector were found to influence the overall fusion enzyme activity. The resulting bifunctional enzyme retained the catalytic properties of both individual enzymes. The lyophilized cell-free extract containing the bifunctional enzyme was applied for the convergent cascade reaction consisting of cyclobutanone and butane-1,4-diol in different microaqueous media with only 5 % (v/v) aqueous buffer without any addition of external cofactor. Methyl tert-butyl ether and cyclopentyl methyl ether were found to be the best organic media for the synthesis of γ-butyrolactone, resulting in about 27 % analytical yield.
REARRANGEMENT OF 2-BUTYNE-1,4-DIOL TO BUTYROLACTONE CATALYZED BY RUTHENIUM COMPLEXES
Shvo, Youval,Blum, Yigal,Reshep, Deborah
, p. C79 - C81 (1982)
The isomerization of 2-butyne-1,4-diol to butyrolactone catalysed by ruthenium complexes is described.
Au/TiO2 as high efficient catalyst for the selective oxidative cyclization of 1,4-butanediol to γ-butyrolactone
Huang, Jie,Dai, Wei-Lin,Li, Hexing,Fan, Kangnian
, p. 69 - 76 (2007)
Au/TiO2 catalysts prepared by the deposition-precipitation method showed excellent activity and selectivity in the oxidative cyclization of 1,4-butanediol to γ-butyrolactone, with high yields (>99%) under mild conditions (413 K, 1.25 MPa air). Catalysts with 3-8% gold loading and calcined at 573-673 K were all highly active for the formation of γ-butyrolactone, as demonstrated by XRD, TEM, XPS, ICP and UV-vis DRS results. It is concluded that highly dispersed small (2-10 nm) gold particles are formed with the surface enrichment of gold. The ratio of cationic gold to metallic gold depends on the treatment temperature. These findings, combined with those of the activity tests, lead to the conclusion that the surface metallic nanosized gold particles are active sites. The catalyst can be reused with no drop in activity or selectivity.
Gas-phase hydrogenation of maleic anhydride to γ-butyrolactone over Cu-CeO2-Al2O3 catalyst at atmospheric pressure: Effects of the residual sodium and water in the catalyst precursor
Yu, Yang,Zhan, Wangcheng,Guo, Yun,Lu, Guanzhong,Adjimi, Souheila,Guo, Yanglong
, p. 392 - 397 (2014)
Cu-CeO2-Al2O3 catalysts were prepared by the co-precipitation method with different washing operations during the preparation process for the purpose of controlling the contents of the residual sodium and water in the catalyst precursors. Cu-CeO2-Al2O3 catalysts were characterized by ICP-AES, XRD, SEM, nitrogen sorption, N2O chemisorption, Raman spectroscopy and H2-TPR. Effects of the residual sodium and water in the catalyst precursor on the catalytic performance of Cu-CeO2-Al2O3 catalyst for gas-phase hydrogenation of maleic anhydride to γ-butyrolactone at atmospheric pressure, and the structure-activity relationships were investigated. The results show that the residual water and sodium in the form of Na2CO3 in the catalyst precursor lead to a decrease in Cu dispersion and Cu surface area, which is disadvantageous to the catalytic performance and stability. Washing step of the residual sodium in the catalyst precursor with the deionized water and then removing step of the residual water using azeotropy distillation shows a great improvement in the stability of Cu-CeO2-Al2O3 catalyst, in which 100% of conversion of maleic anhydride and 100% of selectivity to γ-butyrolactone were maintained for 12 h.
CATALYTIC ENANTIOTOPOS DIFFERENTIATING DEHYDROGENATION OF PROCHIRAL DIOLS USING RUTHENIUM COMPLEX WITH DIOP
Ishii, Youichi,Osakada, Kohtaro,Ikariya, Takao,Saburi, Masahiko,Yoshikawa, Sadao
, p. 1179 - 1182 (1982)
Optically active δ- and γ-lactones are obtained by the homogeneous catalytic dehydrogenation of prochiral diols using Ru2Cl4((-)-DIOP)3 in the presence of benzalacetone as a hydrogen acceptor and triethylamine.
Oxidative heterocyclization of 1,4-butanediol to 4-butanolide
Seleznev,Zorina,Trifonova,Zorin,Rakhmankulov
, p. 1064 - 1065 (2002)
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Hydrolysis of Spiro Derivatives that Undergo No Shrinkage on Polymerization
Tagoshi, Hirotaka,Endo, Takeshi
, p. 945 - 947 (1989)
Acid catalysed hydrolyses of spiroorthoeters (1, 2a, 2b, and 2c and spirocarbonates (3 and 4) were carried out to give the corresponding ring-opening reaction products.The ring-cleavage modes of these spiro derivatives depended on the structure of intermediate cations.
A novel route for synthesis of γ-butyrolactone through the coupling of hydrogenation and dehydrogenation
Zhu, Yu-Lei,Xiang, Hong-Wei,Wu, Gui-Sheng,Bai, Liang,Li, Yong-Wang
, p. 254 - 255 (2002)
A coupling process of the hydrogenation of maleic anhydride and the dehydrogenation of 1,4-butanediol has been invented for the synthesis of γ-butyrolactone over a Cu-Zn catalyst, realizing optimal hydrogen utilization and better energy efficiency.
OXIDATION OF CYCLOBUTANONES TO γ-BUTYROLACTONES WITH HYDROGEN PEROXIDE IN 2,2,2-TRIFLUOROETHANOL
Matsumoto, Masakatsu,Kobayashi, Hisako
, p. 2443 - 2447 (1986)
Cyclobutanones were selectively oxidized to yield γ-butyrolactones with hydrogen peroxide in 2,2,2-trifluoroethanol.
Routes to Heterotrinuclear Metal Siloxide Complexes for Cooperative Activation of O2
Braun-Cula, Beatrice,Herwig, Christian,Hoof, Santina,Limberg, Christian,Wind, Marie-Louise
, (2020)
The assembly of heterometallic complexes capable of activating dioxygen is synthetically challenging. Here, we report two different approaches for the preparation of heterometallic superoxide complexes [PhL2CrIII-η1-O2][MX]2 (PhL = -OPh2SiOSiPh2O-, MX+ = [CoCl]+, [ZnBr]+, [ZnCl]+) starting from the CrII precursor complex [PhL2CrII]Li2(THF)4. The first strategy proceeds via the exchange of Li+ by [MX]+ through the addition of MX2 to [PhL2CrII]Li2(THF)4 before the reaction with dioxygen, whereas in the second approach a salt metathesis reaction is undertaken after O2 activation by adding MX2 to [PhL2CrIII-η1-O2]Li2(THF)4. The first strategy is not applicable in the case of redox-active metal ions, such as Fe2+ or Co2+, as it leads to the oxidation of the central chromium ion, as exemplified with the isolation of [PhL2CrIIICl][CoCl]2(THF)3. However, it provided access to the hetero-bimetallic complexes [PhL2CrIII-η1-O2][MX]2 ([MX]+ = [ZnBr]+, [ZnCl]+) with redox-inactive flanking metals incorporated. The second strategy can be applied not only for redox-inactive but also for redox-active metal ions and led to the formation of chromium(III) superoxide complexes [PhL2CrIII-η1-O2][MX]2 (MX+ = [ZnCl]+, [ZnBr]+, [CoCl]+). The results of stability and reactivity studies (employing TEMPO-H and phenols as substrates) as well as a comparison with the alkali metal series (M+ = Li+, Na+, K+) confirmed that although the stability is dependent on the Lewis acidity of the counterions M and the number of solvent molecules coordinated to those, the reactivity is strongly dependent on the accessibility of the superoxide moiety. Consequently, replacement of Li+ by XZn+ in the superoxides leads to more stable complexes, which at the same time behave more reactive toward O-H groups. Hence, the approaches presented here broaden the scope of accessible heterometallic O2 activating compounds and provide the basis for further tuning of the reactivity of [RL2CrIII-η1-O2]M2 complexes.
Ru/SiO2 Catalyst for Highly Selective Hydrogenation of Dimethyl Malate to 1,2,4-Butanetriol at Low Temperatures in Aqueous Solvent
Chen, Can,Jiang, Junxiang,Li, Guangci,Li, Xuebing,Wang, Da,Wang, Zhong,Yu, Pei
, (2022/01/12)
Catalytic selective hydrogenation of esterified malic acid to produce 1,2,4-butanetriol (1,2,4-BT) using H2 as the reducing reagent suffers from the low 1,2,4-BT selectivity. Here, Ru/SiO2 catalyst was employed for selective hydrogenation of dimethyl malate (DM) to produce 1,2,4-BT, which gave abnormal high DM conversion (100%) and 1,2,4-BT selectivity (92.4%) in aqueous solvent at 363?K, especially, the 1,2,4-BT yield even is higher than the optimal catalyst reported (Ru-Re, 79.8%). The reaction pathways for the DM hydrogenation on Ru/SiO2 were also proposed, suggesting that extremely high 1,2,4-BT selectivity require for the much high hydrogenation rates at low temperatures, where side-reaction transesterification rates are relatively low. The extremely high hydrogenation activity and 1,2,4-BT selectivity on Ru/SiO2 in aqueous solvent at low temperatures arise from that H2O may coordinate to Ru2+ and prevent the reduction of Ru2+ to Ru under high H2 pressure. Ru/SiO2 surface presents abundant Ru2+ in aqueous solvent, can activate H2 through heterolytic cleavage mode to form hydride, which can significantly increase hydrogenation rates of C = O groups at low temperatures. In addition, the activity and 1,2,4-BT selectivity on Ru/SiO2 catalyst only reduced by 2.3% and 2.6%, respectively over a period of 550?h. Graphical Abstract: [Figure not available: see fulltext.]
Catalytic behaviour of the Cu(I)/L/TEMPO system for aerobic oxidation of alcohols - a kinetic and predictive model
Abu-Radaha, Batool,Al-Hunaiti, Afnan,Repo, Timo,Wraith, Darren
, p. 7864 - 7871 (2022/04/09)
Here, we disclose a new copper(i)-Schiff base complex series for selective oxidation of primary alcohols to aldehydes under benign conditions. The catalytic protocol involves 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), N-methylimidazole (NMI), ambient air, acetonitrile, and room temperature. This system provides a straightforward and rapid pathway to a series of Schiff bases, particularly, the copper(i) complexes bearing the substituted (furan-2-yl)imine bases N-(4-fluorophenyl)-1-(furan-2-yl)methanimine (L2) and N-(2-fluoro-4-nitrophenyl)-1-(furan-2-yl)methanimine (L4) have shown excellent yields. Both benzylic and aliphatic alcohols were converted to aldehydes selectively with 99% yield (in 1-2 h) and 96% yield (in 16 h). The mechanistic studies via kinetic analysis of all components demonstrate that the ligand type plays a key role in reaction rate. The basicity of the ligand increases the electron density of the metal center, which leads to higher oxidation reactivity. The Hammett plot shows that the key step does not involve H-abstraction. Additionally, a generalized additive model (GAM, including random effect) showed that it was possible to correlate reaction composition with catalytic activity, ligand structure, and substrate behavior. This can be developed in the form of a predictive model bearing in mind numerous reactions to be performed or in order to produce a massive data-set of this type of oxidation reaction. The predictive model will act as a useful tool towards understanding the key steps in catalytic oxidation through dimensional optimization while reducing the screening of statistically poor active catalysis.