- Fully utilizing seeds solution for solvent-free synthesized nanosized TS-1 zeolites with efficient epoxidation of chloropropene
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Nanosized titanium silicalite-1 (TS-1) demonstrates excellent catalytic ability in the selective catalytic oxidation reaction. However, their synthesis process is usually complicated with low yield under hydrothermal conditions, which is not in line with the concept of green chemistry. Herein, via fully utilizing untreated seeds solution, we report firstly an entirely green strategy for solvent-free synthesizing anatase-free nanosized TS-1 zeolite. The success lies in the fully utilization of seeds solution which is composed of supersaturated structure directing agent (TPAOH), unreacted silica source, water and formed MFI seeds (silicalite-1) without external purification. In the followed solvent-free synthesis of final nanosized TS-1 product, no additional TPAOH is added, which greatly reduces the synthesis cost and synthetic procedure and maintains a high product yield. The obtained nanosized TS-1 zeolite without anatase phase has high crystallinity, large specific surface area. More importantly, the nanosized TS-1 (Si/Ti ?= ?77) catalysts exhibit excellent catalytic ability for the epoxidation of chloropropene with 40.0% conversion and 97.6% selectivity. This sustainable and green synthesis method opens up a new way to regulate nanosized zeolite.
- Chai, Yongming,Li, Bin,Li, Yichuan,Liu, Hanfang,Liu, Jia,Liu, Yanru,Ran, Saisai,Wang, Fupeng,Wang, Lei,Wang, Yu,Xie, Huijie,Ye, Tiantian
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- An Amphiphilic (salen)Co Complex – Utilizing Hydrophobic Interactions to Enhance the Efficiency of a Cooperative Catalyst
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An amphiphilic (salen)Co(III) complex is presented that accelerates the hydrolytic kinetic resolution (HKR) of epoxides almost 10 times faster than catalysts from commercially available sources. This was achieved by introducing hydrophobic chains that increase the rate of reaction in one of two ways – by enhancing cooperativity under homogeneous conditions, and increasing the interfacial area under biphasic reaction conditions. While numerous strategies have been employed to increase the efficiency of cooperative catalysts, the utilization of hydrophobic interactions is scarce. With the recent upsurge in green chemistry methods that conduct reactions ‘on water’ and at the oil-water interface, the introduction of hydrophobic interactions has potential to become a general strategy for enhancing the catalytic efficiency of cooperative catalytic systems. (Figure presented.).
- Solís-Mu?ana, Pablo,Salam, Joanne,Ren, Chloe Z.-J.,Carr, Bronte,Whitten, Andrew E.,Warr, Gregory G.,Chen, Jack L.-Y.
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supporting information
p. 3207 - 3213
(2021/06/01)
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- Selective synthesis of epichlorohydrin: Via liquid-phase allyl chloride epoxidation over a modified Ti-MWW zeolite in a continuous slurry bed reactor
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The epoxidation of allyl chloride (ALC) to epichlorohydrin (ECH) with H2O2 using a piperidine (PI)-modified Ti-MWW catalyst (Ti-MWW-PI) in a continuous slurry reactor was investigated to develop an efficient reaction system for the corresponding industrial process. The reaction parameters, including solvent, reaction temperature, t-butanol/ALC mass ratio, ALC/H2O2 molar ratio, weight hourly space velocity of H2O2, and the addition amount of ammonia, were studied in detail to pursue high H2O2 conversion and ECH selectivity. A long catalytic lifetime of 244 h was achieved at high H2O2 conversion (>97.0%) and ECH selectivity (>99.8%) under optimized reaction conditions. The crystallinity was well maintained for the deactivated Ti-MWW-PI catalyst, which was regenerated by a combination of calcination and piperidine treatment. This journal is
- Ding, Luoyi,Yin, Jinpeng,Tong, Wen,Peng, Rusi,Jiang, Jingang,Xu, Hao,Wu, Peng
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p. 331 - 342
(2021/01/11)
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- RUTHENIUM COMPLEX AND PRODUCTION METHOD THEREOF, CATALYST, AND PRODUCTION METHOD OF OXYGEN-CONTAINING COMPOUND
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PROBLEM TO BE SOLVED: To provide a ruthenium complex that is particularly useful as a catalyst for oxidizing a substrate having a carbon-hydrogen bond. SOLUTION: The ruthenium complex represented by the general formula (i) or a cis conformer thereof is provided. In the general formula (i), R1 represents H, a phenyl group or a substituted phenyl group; R2 represents H, a phenyl group or an alkyl group; L1 represents halogen or water molecule; L2 represents triphenylphosphine, pyridine, imidazole or dimethylsulfoxide; X represents halogen; and n represents 1 or 2. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
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Paragraph 0145-0148
(2021/01/29)
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- Epoxidation of Allyl Chloride in the Presence of Tungsten Oxo–Peroxo Heteropoly Compounds of P(V), As(V), and Si(IV) Under Phase-Transfer Catalysis Conditions
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Abstract: This study investigates the behavior of nonmetals in tungsten oxo–peroxoheteropoly compounds in the reaction of allyl chloride epoxidation. Thecatalytic efficiency in epoxidation was shown to increase in the followingorder: Si(IV) As(V) P(V). Synergism in allyl chloride epoxidation wasdemonstrated for the first time for mixtures of tungsten oxo–peroxo heteropolycompounds of P and As, as well as P and Si. It was also shown that mixturesconsisting of 70% P + 30% Si and 75% P + 25% As exhibit the highest catalyticactivity. Finally, the article suggests a mechanism for the synergisticeffect. [Figure not available: see fulltext.].
- Panicheva,Meteleva,Ageikina,Panichev
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p. 1270 - 1274
(2021/10/20)
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- A method for efficient preparation of epichlorohydrin by biomass glycerol
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The present invention discloses a method for efficiently preparing epichlorohydrin by biomass glycerol, comprising the following steps: 1) the mass ratio of 1: 0.06 ~ 0.08 of biomass glycerol and a composite catalyst poured into the reactor, and then using an ultrasonic probe to extend into the reactor, 2) step 1) after the end of the reaction, the resulting material is cooled to room temperature and transferred to the reaction vessel, maintaining a temperature of 15 ~ 30 ° C, and then adding an alkaline cyclizer for the reaction; 3) after the completion of the reaction to filter the resulting solids, The filtrate is a solution of epichlorohydrin oxide; the glycerol of the present invention can be completely converted, the intermediate product dichloropropanol yield is high, and the selectivity of collecting 1,3-dichloropropanol is improved, which accelerates the reaction rate; and the process can be co-produced with biodiesel and chlor-alkali industry, and the industrialization prospect is good.
- -
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Paragraph 0040-0041; 0051-0052; 0062-0063; 0073
(2022/01/10)
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- Mixed tetradentate NHC/1,2,3-triazole iron complexes bearing cis labile coordination sites as highly active catalysts in Lewis and Br?nsted acid mediated olefin epoxidation
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Two bio-inspired non-heme iron complexes bearing mixed tetradentate N-heterocyclic carbene/1,2,3-triazole ligands with cis labile coordination sites are reported. The compounds are studied in olefin epoxidation catalysis using H2O2 as oxidant. Sc(OTf)3, HClO4 and HOAc are applied as additives resulting in significant improvement of catalytic performance. Under optimized conditions the most active catalyst exhibits activities of 76,000 turnovers per hour, which is the highest reported value for an iron(II) catalyst. The complexes reveal comparably high stability and enable the challenging epoxidation of functionalized olefins. These results prove 1,2,3-triazoles to be promising and tunable ligands for iron catalyzed oxidation reactions.
- Dyckhoff, Florian,Jakob, Christian H. G.,Kühn, Fritz E.,Nguyen, Linda,Reich, Robert M.,Schlagintweit, Jonas F.
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p. 144 - 152
(2020/02/04)
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- Controlling the Morphology and Titanium Coordination States of TS-1 Zeolites by Crystal Growth Modifier
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Developing an effective strategy to synthesize perfect titanosilicate TS-1 zeolite crystals with desirable morphologies, enriched isolated framework Ti species, and thus enhanced catalytic oxidation properties is a pervasive challenge in zeolite crystal engineering. We here used an amino acid l-carnitine as a crystal growth modifier and ethanol as a cosolvent to regulate the morphologies and the Ti coordination states of TS-1 zeolites. During the hydrothermal crystallization process, the introduced l-carnitine can not only tailor the anisotropic growth rates of zeolite crystals but also induce the formation of uniformly distributed framework Ti species through building a suitable chemical interaction with the Ti precursor species. Condition optimizations could afford the generation of perfect hexagonal plate TS-1 crystals and elongated platelet TS-1 crystals enriched in tetrahedral framework Ti sites (TiO4) or mononuclear octahedrally coordinated Ti species (TiO6). Both samples showed significant improvement in catalytic activity for the H2O2-mediated epoxidation of alkenes. In particular, the elongated platelet TS-1 enriched in "TiO6"species afforded the highest activity in 1-hexene epoxidation, with a turnover frequency (TOF) of up to 131 h-1, which is approximately twice as high as that of the conventional TS-1 zeolite (TOF: 65 h-1) and even higher than those of the literature-reported TiO6-containting TS-1 catalysts derived from the hydrothermal post-treatment of TS-1 zeolites. This work demonstrates that the morphologies and the titanium coordination states of TS-1 zeolites can be effectively tuned by directly introducing suitable crystal growth modifiers, thus providing new opportunities for developing highly efficient titanosilicate zeolite catalysts for important catalytic applications.
- Chang, Xinyu,Chen, Ziyi,Hu, Dianwen,Jia, Mingjun,Li, Yingying,Song, Xiaojing,Yang, Xiaotong,Yu, Jihong,Zhang, Hao,Zhang, Peng,Zhang, Qiang,Zhang, Tianjun
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supporting information
p. 13201 - 13210
(2020/10/02)
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- Visible-light assisted of nano Ni/g-C3N4 with efficient photocatalytic activity and stability for selective aerobic C?H activation and epoxidation
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A selective, economical, and ecological protocol has been described for the oxidation of methyl arenes and their analogs to the corresponding carbonyl compounds and epoxidation reactions of alkenes with molecular oxygen (O2) or air as a green oxygen source, under mild reaction conditions. The nano Ni/g-C3N4 exhibited high photocatalytic activity, stability, and selectivity in the C?H activation of methyl arenes, methylene arenes, and epoxidation of various alkenes under visible- light irradiation without the use of an oxidizing agent and under base free conditions.
- Akrami, Zahra,Hosseini-Sarvari, Mona
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supporting information
(2020/10/13)
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- Epoxidation of allyl chloride with H2O2 catalyzed by three structurally related quaternary ammonium modified polyoxophosphotungstates
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The one-step epoxidation of allyl chloride has always been a great challenge for the industrial production. The key of this technology is to find efficient and friendly catalyst. In this paper, three structurally related quaternary ammonium modified polyoxophosphotungstates were synthesized by green and facile method. Among them, [C16H33(CH3)3N]3PW4O24 and [π-C5H5NC16H33]3PW4O24 are reaction-controlled phase transfer catalyst (RPTC) and [(C18H37)2(CH3)2N]3PW4O24 is temperature-controlled phase transfer catalyst (TPTC). All three catalysts could achieve the epoxidation of allyl chloride with equimolar H2O2 under solvent-free and mild conditions. Moreover, the catalysts exhibited excellent catalytic performance and reusability. The catalytic mechanism was explored by FT-IR spectroscopy. The results of kinetic experiments show that the chain length of alkanes and heterocyclic structure of cations have a great influence on the catalytic activity of the catalysts.
- Cui, Yu,Jiang, Xuchuan,Sun, Guoxin,Sun, Junhua,You, Qi,Zhao, Xiuxian
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- Exploring the Biocatalytic Scope of a Novel Enantioselective Halohydrin Dehalogenase from an Alphaproteobacterium
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A gene encoding halohydrin dehalogenase from an alphaproteobacterium (AbHHDH) was identified, cloned and over-expressed in Escherichia coli. AbHHDH was able to catalyze the stereoselective dehalogenation of prochiral and racemic halohydrins. It showed the highest enantioselectivity in the dehalogenation of 20?mM (R,S)-2-bromo-1-phenylethanol, which yielded (S)-2-bromo-1-phenylethanol with 99% ee and 34.5% yield. Moreover, AbHHDH catalyzed the azidolysis of epoxides with low to moderate (S)-enantioselectivity. The highest enantioselectivity (E = 18.6) was observed when (R,S)-benzyl glycidyl ether was used as the substrate. A sequential kinetic resolution catalyzed by HHDH was employed for the synthesis of chiral 1-chloro-3-phenoxy-2-propanol. We prepared enantiopure (S)-isomer with a high enantiopurity of ee > 99% and a yield of 30.7% (E-value: 21.3) by kinetic resolution of 20?mM substrate. The (S)-isomer with 99% ee readily obtained from 40 to 150?mM (R,S)-1-chloro-3-phenoxy-2-propanol. Taken together, the results of this study demonstrate the applicability of this HHDH for the production of optically active compounds. [Figure not available: see fulltext.].
- Xue, Feng,Ya, Xiangju,Xiu, Yuansong,Tong, Qi,Wang, Yuqi,Zhu, Xinhai,Huang, He
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p. 629 - 637
(2019/01/25)
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- Aromatic donor-acceptor interaction promoted catalyst assemblies for hydrolytic kinetic resolution of epichlorohydrin
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Three generations of Co(iii)-salen complexes containing electron-deficient aromatic moieties (acceptors) have been synthesized. When electron-rich aromatic compounds (donors) were introduced, these complexes were designed to form catalyst assemblies through aromatic donor-acceptor interaction. For all three generations of complexes, the addition of a proper donor led to higher catalytic efficiency in the hydrolytic kinetic resolution (HKR) of epichlorohydrin. The reaction rates are in the following order: Generation 3 > Generation 2 > Generation 1. The aromatic donor-acceptor interaction was verified by NMR spectroscopy and UV-vis absorption spectroscopy studies. These results demonstrated that aromatic donor-acceptor interaction can be a valuable driving force in the assembly of supramolecular catalysts.
- Blechschmidt, Daniel R.,Woodhouse, Matthew D.,Inagaki, Sebastien,Whitfield, Melita,Ogunsanya, Ayokunnumi,Yoder, Aaron,Lilly, Daniel,Heim, Eric W.,Soucie, Luke N.,Liang, Jian,Liu, Yu
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supporting information
p. 172 - 180
(2019/01/04)
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- Molecular modification of a halohydrin dehalogenase for kinetic regulation to synthesize optically pure (S)-epichlorohydrin
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Asymmetric synthesis of chiral epichlorohydrin (ECH) from 1,3-dichloro-2-propanol (1,3-DCP) using halohydrin dehalogenases (HHDHs) is of great value due to the 100% theoretical yield and high enantioselectivity. The vital problem in the asymmetric synthesis is to prepare optically pure ECH. In this study, key amino acid residues located at halide ion channels of HheC (P175S/W249P) (HheCPS) were modified to regulate the kinetic parameters. HheCPS I81W, F86N and V94R were constructed with the corresponding halide ion channels destroyed. The catalytically efficiencies (kcat/Km) of the three mutants exhibited 0.38-, 0.23- and 0.23-fold decrease toward (S)-ECH and the reverse reaction was significantly inhibited. As the results, (S)-ECH was synthesized with >99% enantiomeric excess (e.e.) and 63.42%, 67.08% and 57.01% yields, respectively, under 20 mM 1,3-DCP as substrate. To our knowledge, this is the first investigation of the molecule kinetic modification of HHDHs and also the first report for the biosynthesis of optically pure (S)-ECH from 1,3-DCP using HHDHs.
- Zhang, Xiao-Jian,Deng, Han-Zhong,Liu, Nan,Gong, Yi-Chuan,Liu, Zhi-Qiang,Zheng, Yu-Guo
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p. 154 - 160
(2019/01/08)
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- Aromatic Donor-Acceptor Interaction-Based Co(III)-salen Self-Assemblies and Their Applications in Asymmetric Ring Opening of Epoxides
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Aromatic donor-acceptor interaction as the driving force to assemble cooperative catalysts is described. Pyrene/naphthalenediimide functionalized Co(III)-salen complexes self-assembled into bimetallic catalysts through aromatic donor-acceptor interactions and showed high catalytic activity and selectivity in the asymmetric ring opening of various epoxides. Control experiments, nuclear magnetic resonance (NMR) spectroscopy titrations, mass spectrometry measurement, and X-ray crystal structure analysis confirmed that the catalysts assembled based on the aromatic donor-acceptor interaction, which can be a valuable noncovalent interaction in supramolecular catalyst development.
- Liang, Jian,Soucie, Luke N.,Blechschmidt, Daniel R.,Yoder, Aaron,Gustafson, Addie,Liu, Yu
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supporting information
p. 513 - 518
(2019/01/14)
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- Method for comprehensively utilizing epichlorohydrin rectification kettle residues
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The present invention relates to a method for comprehensively utilizing epichlorohydrin rectification kettle residues, and concretely relates to a method for regenerating a deactivated heteropolyacidcatalyst recovered from the epichlorohydrin rectification kettle residues. The method mainly has the following advantages: (1) the process is simple to operate, realizes the separation and comprehensive utilization of organic matters and inorganic matters, and has strong enforceability; (2) the production of dangerous solid wastes in the production process of epichlorohydrin is basically avoided;and (3) the kettle residues are fully used to produce value-added products, so economic benefits are brought for the enterprise, and the method is both economical and environmentally friendly.
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Paragraph 0043-0047
(2019/09/16)
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- Diastereoselective Desymmetrization of p-Quinamines through Regioselective Ring Opening of Epoxides and Aziridines
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A highly diastereoselective desymmetrization of p-quinamines via regioselective ring opening of epoxides and aziridines under mild conditions has been developed. A chairlike six-membered transition state with minimized 1,3-diaxial interactions explains the relative stereoselectivity of the cyclization reaction. This transition-metal free [3 + 3] annulation reaction provides rapid access to fused bicyclic morpholines and piperazines with a tetrasubstituted carbon center in high yields. In addition, it also allows the synthesis of enantioenriched products by using easily accessible chiral nonracemic epoxides and aziridines.
- Jadhav, Sandip B.,Chegondi, Rambabu
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supporting information
p. 10115 - 10119
(2019/12/24)
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- Highly selective and efficient olefin epoxidation with pure inorganic-ligand supported iron catalysts
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Over the past two decades, there have been major developments in the transition iron-catalyzed selective oxidation of alkenes to epoxides; a common structure found in drug, isolated natural products, and fine chemicals. Many of these approaches have enabled highly efficient and selective epoxidation of alkenes via the design of specialized ligands, which facilitates to control the activity and selectivity of the reactions catalyzed by iron atom. Herein, we report the development of the olefin epoxidation with inorganic-ligand supported iron-catalysts using 30% H2O2 as an oxidant, and the mechanism is similar to iron-porphyrin type. With the catalyst 1, (NH4)3[FeMo6O18(OH)6], various aromatic and aliphatic alkenes were successfully transformed into the corresponding epoxides with excellent yields as well as chemo- and stereo-selectivity. This catalytic system possesses the advantages of being able to avoid the use of expensive, toxic, air/moisture sensitive and commercially unavailable organic ligands. The generality of this methodology is simple to operate and exhibits high catalytic activity as well as excellent stability, which gives it the potential to be used on an industrial scale, and maybe opens a way for the catalytic oxidation reaction via inorganic-ligand coordinated iron catalysis.
- Zhou, Zhuohong,Dai, Guoyong,Ru, Shi,Yu, Han,Wei, Yongge
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supporting information
p. 14201 - 14205
(2019/10/02)
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- Continuous flow upgrading of glycerol toward oxiranes and active pharmaceutical ingredients thereof
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A robust continuous flow procedure for the transformation of bio-based glycerol into high value-added oxiranes (epichlorohydrin and glycidol) is presented. The flow procedure features a central hydrochlorination/dechlorination sequence and provides economically and environmentally favorable conditions involving an organocatalyst and aqueous solutions of hydrochloric acid and sodium hydroxide. Pimelic acid (10 mol%) shows an exceptional catalytic activity (>99% conversion of glycerol, a high selectivity toward 1,3-dichloro-2-propanol and 81% cumulated yield toward intermediate chlorohydrins) for the hydrochlorination of glycerol (140 °C) with 36 wt% aqueous HCl. These conditions are validated on a sample of crude bio-based glycerol. The dechlorination step is effective (quantitative conversion based on glycerol) with concentrated aqueous sodium hydroxide (20 °C) and can be directly concatenated to the hydrochlorination step, hence providing a ca. 2:3 separable mixture of glycidol and epichlorohydrin (74% cumulated yield). An in-line membrane separation unit is included downstream, providing usable streams of epichlorohydrin (in MTBE, with an optional concentrator) and glycidol (in water). The scalability of the dechlorination step is then assessed in a commercial pilot-scale continuous flow reactor. Next, bio-based epichlorohydrin is further utilized for the continuous flow preparation of β-amino alcohol active pharmaceutical ingredients including propranolol (hypertension, WHO essential), naftopidil (prostatic hyperplasia) and alprenolol (angina pectoris) within a concatenable two-step procedure using a FDA class 3 solvent (DMSO). This work provides the first example of direct upgrading of bio-based glycerol into high value-added pharmaceuticals under continuous flow conditions.
- Morodo, Romain,Gérardy, Romaric,Petit, Guillaume,Monbaliu, Jean-Christophe M.
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p. 4422 - 4433
(2019/08/21)
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- Imido-P(v) trianion supported enantiopure neutral tetrahedral Pd(II) cages
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Charge-neutral chiral hosts are attractive due to their ability to recognize a wide range of guest functionalities and support enantioselective processes. However, reports on such charge-neutral cages are very scarce in the literature. Here, we report an enantiomeric pair of tetrahedral Pd(ii) cages built from chiral tris(imido)phosphate trianions and oxalate linkers, which exhibit enantioselective separation capabilities for epichlorohydrin, β-butyrolactone, and 3-methyl- and 3-ethyl cyclopentanone.
- Rajasekar, Prabhakaran,Pandey, Swechchha,Paithankar, Harshad,Chugh, Jeetender,Steiner, Alexander,Boomishankar, Ramamoorthy
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supporting information
p. 1873 - 1876
(2018/02/23)
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- Homochiral Metal-Organic Cage for Gas Chromatographic Separations
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Metal-organic cages (MOCs) as a new type of porous material with well-defined cavities were extensively pursued because of their relative ease of synthesis and their potential applications in host-guest chemistry, molecular recognition, separation, catalysis, gas storage, and drug delivery. Here, we first reported that a homochiral MOC [Zn3L2] is explored to fabricate [Zn3L2] coated capillary column for high-resolution gas chromatographic separation of a wide range of analytes, including n-alkanes, polycyclic aromatic hydrocarbons, and positional isomers, especially for racemates. Various kinds of racemates such as alcohols, diols, epoxides, ethers, halohydrocarbons, and esters were separated with good enantioselectivity and reproducibility on the [Zn3L2] coated capillary column. The fabricated [Zn3L2] coated capillary column exhibited significant chiral recognition complementary to that of a commercial β-DEX 120 column and our recently reported homochiral porous organic cage CC3-R coated column. The results show that the homochiral MOCs will be very attractive as a new type of chiral selector in separation science.
- Xie, Sheng-Ming,Fu, Nan,Li, Li,Yuan, Bao-Yan,Zhang, Jun-Hui,Li, Yan-Xia,Yuan, Li-Ming
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p. 9182 - 9188
(2018/07/21)
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- Synthetic method of epoxide
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The invention discloses a synthetic method of epoxide. Hydrogen peroxide is used as an oxidant, and a catalytic system consisting of a catalyst and solvent is used for catalyzing a reactant comprisinga carbon-carbon double bonds and at least one other functional group to synthesize the epoxide; in the catalytic system, the solvent is a mixture of alcohol and water, and the catalyst is a metal ionmodified mixture consisting of an MWW structure titanium silicon molecular sieve and a carrier; and the weight percent of the titanium silicon molecular sieve in the catalyst is not less than 20 percent of the total weight of the catalyst, the type of metal ions is expressed as MXO by virtue of a molecular expression of metal oxide, wherein X is equal to 1 or 2, the weight percent is 0.05 to 3 percent of the total weight of the catalyst by calculating with the content of metal atoms M, and the carrier is at least one of silicon dioxide, aluminum oxide and aluminum phosphate with the balance weight. By utilizing the catalyst system, the epoxide can be high actively and high selectively synthesized in a catalytic manner; and the reaction process is simple and environment-friendly, the energy consumption is low, and the industrialized production and application are easy.
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Paragraph 0020; 0034; 0035; 0036; 0047; 0048; 0049
(2018/10/11)
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- APPARATUS AND METHOD FOR MANUFACTURING EPICHLOROHYDRIN BY REACTING ALLYL CHLORIDE AND HYDROGEN PEROXIDE
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An apparatus for manufacturing epichlorohydrin including at least one reactor, a supply device of allyl chloride , a supply device of hydrogen peroxide aqueous solution, a distillation column and a decanter. The supply device of allyl chloride is connected to the reactor. The supply device of hydrogen peroxide aqueous solution is connected to the reactor. The distillation column is connected to a product outlet of the reactor. The decanter is connected to a bottom portion of the distillation column to form an aqueous phase product and an organic phase product including epichlorohydrin.
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Paragraph 0036; 0037; 0038; 0039; 0040
(2018/09/02)
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- New perspective to catalytic epoxidation of olefins by Keplerate containing Keggin polyoxometalates
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Different Keggin encapsulated in Keplerate polyoxometalates (Mo72Fe30, PMo12 ? Mo72Fe30, SiMo12 ? Mo72Fe30 and BW12 ? Mo72Fe30) have been synthesized and their catalytic efficiency in the epoxidation of olefins with hydrogen peroxide investigated. Results were confirmed that Keggin encapsulated in Keplerates could show higher catalytic activity than parent ones. These POM catalysts lead to heterogeneous epoxidation of alkenes by hydrogen peroxide with green features of convenient recovery, steady reuse, high conversion and selectivity, and simple preparation.
- Taghiyar, Hamid,Yadollahi, Bahram
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supporting information
p. 98 - 104
(2018/10/05)
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- Phase Transfer of the Organic Substrate in the Epoxidation Reaction of Allyl Chloride in Two-Phase Aqueous–Organic Systems
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Abstract: The mechanism of synergism for mixtures of phase-transfer carriers QХ with tertiary amines and pyridine in the epoxidation reaction of allyl chloride has been established. It has been shown that tertiary amines (triethylamine, tributylamine, N,N-dimethylaniline, and N-methyldiethanolamine) and pyridine oxidizable in situ to N-oxides promote the transfer of the organic substrate (allyl chloride) to the interface (PB). It is assumed that the synergism of mixtures of phase-transfer carriers QХ with a tertiary amine oxide or pyridine oxide can also be due to the formation of a mixture of two catalysts, Q3[PW4O24] and WO(O2)2L (where L = a tertiary amine oxide or pyridine oxide). The WO(O2)2L complex will provide the stage of reoxidation of the complex Q3[PW4O24 ?х] in the organic phase and, hence, the possibility for the development of the process of epoxidation not only at the interface but also in the bulk of the organic phase. The maximum coefficient of synergistic effect (ks = 2) is observed for a mixture of cetylpyridinium bromide (90 mol %) and pyridine N-oxide (10 mol %).
- Panicheva,Meteleva,Ageikina,Panichev
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p. 884 - 888
(2018/10/15)
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- Synthesis, crystal structure and catalytic property of a dinuclear cobalt(III) complex derived from 2-ethyl-2-{[1-(2-hydroxy-5-methylphenyl)methylidene]amino}propane-1,3-diol
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With a tetradentate Schiff base ligand 2-ethyl-2-{[1-(2-hydroxy-5-methylphenyl)methylidene]amino}propane-1,3-diol (H3L) with cobalt nitrate and ammonium thiocyanate, a dinuclear cobalt(III) complex was prepared and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. The complex crystallizes in the monoclinic space group P21/n with unit cell dimensions a = 17.682(2) ?, b = 22.652(2) ?, c = 18.617(2) ?, β = 99.546(2)°, V = 7,353.5(12) ?3, Z = 4, R1 = 0.0956, and wR2 = 0.2027. Single crystal X-ray diffraction analysis reveals that the asymmetric unit of the compound contains two dinuclear cobalt(III) complex molecules, three methanol molecules and one water molecule of crystallization. The Co???Co distances in the dinuclear cobalt(III) complex molecules are about 2.97 ?. The Co atoms are in octahedral coordination. The complex has effective property on the oxidation of various aliphatic and aromatic olefins.
- Qiu, Xiao-Yang
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p. 182 - 186
(2018/09/25)
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- Synthesis method of intermediate epoxidized aminobenzene butane
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The invention discloses a synthesis method of intermediate epoxidized aminobenzene butane. The synthesis method includes: taking chlorine, isopropyl alcohol, chlorohydrin, potassium carbonate, citricacid, SBA-15 molecular sieve and MnO2 as main raw materials; removing a molecular hydrogen chloride under alkaline condition by adopting chlorohydrin and performing cyclization to obtain the final epoxidized aminobenzene butane. With the method, moderate reaction condition is achieved, side reaction of the product is generated under the strong alkaline condition, generation of side reaction is effectively inhibited by using an MnO2/SBA-15 catalyst, yield of reaction is increased, synthesis time is shortened, and research basis and industrial application value are provided for industrializationof protease inhibitor drugs.
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Paragraph 0008; 0019-0028
(2018/10/19)
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- Towards sustainable manufacture of epichlorohydrin from glycerol using hydrotalcite-derived basic oxides
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Commercial two-step processes to convert glycerol into epichlorohydrin are more benign compared to the predominant industrial route starting from propene in terms of materials requirements and CO2 emissions. Still, the use of alkali hydroxides in stoichiometric amounts in the second reaction, i.e., the dehydrochlorination of the dichloropropanol intermediate, leads to the formation of large amounts of salt wastes, thus limiting the greenness of the technology. Here, we show for the first time that the latter transformation can be selectively conducted in the gas phase in the presence of a heterogeneous hydrotalcite-derived mixed oxide of Al and Mg. Upon reaction, the lamellar solid is rehydrated to a hydrotalcite-like compound, which can effectively activate the alcoholic group of dichloropropanol owing to its strong Br?nsted basic character and moderately high surface area. In-depth characterisation of the porous, compositional, structural and acid/base properties demonstrates that the HCl formed during the reaction causes the progressive exchange of interlayer OH groups by Cl atoms, thus gradually diminishing the reactivity of the material. Facile calcination restores the original mixed oxide structure and is shown to enable three equivalent consecutive reaction runs. Since the HCl evolved along with water upon regeneration can be recycled in the first step of the process, i.e., glycerol hydrochlorination, our approach paves the way for a waste-free and more atom efficient biobased epichlorohydrin production process.
- Lari, Giacomo M.,Pastore, Giorgio,Mondelli, Cecilia,Pérez-Ramírez, Javier
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supporting information
p. 148 - 159
(2018/01/12)
-
- Asymmetric Hydrolytic and Aminolytic Kinetic Resolution of Racemic Epoxides using Recyclable Macrocyclic Chiral Cobalt(III) Salen Complexes
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New chiral macrocyclic cobalt(III) salen complexes were synthesized and used as catalyst for the asymmetric kinetic resolution (AKR) of terminal epoxides and glycidyl ethers with aromatic/aliphatic amines and water as nucleophiles. This is the first occasion where a Co(III) salen complex demonstrated its ability to catalyze AKR as well as hydrolytic kinetic resolution (HKR) reactions. Excellent enantiomeric excesses of the epoxides, the corresponding amino alcohols and diols (upto 99%) with quantitative yields were achieved by using the chiral Co(III) salen complexes in dichloromethane at room temperature. This protocol was further extended for the synthesis of two important drug molecules, i.e., (S)-propranolol and (R)-naftopidil. The catalytic system was also explored for the synthesis of chirally pure diols and chiral cyclic carbonates using carbon dioxide as a greener renewable C1 source. The catalyst was recycled for upto 5 catalytic cycles with retention of enantioselectivity. (Figure presented.).
- Tak, Rajkumar,Kumar, Manish,Menapara, Tusharkumar,Gupta, Naveen,Kureshy, Rukhsana I.,Khan, Noor-ul H.,Suresh
-
supporting information
p. 3990 - 4001
(2017/11/22)
-
- Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions
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The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.
- Xia, Qingchun,Li, Zijian,Tan, Chunxia,Liu, Yan,Gong, Wei,Cui, Yong
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supporting information
p. 8259 - 8266
(2017/06/28)
-
- Efficient Catalytic System Involving Molybdenyl Acetylacetonate and Immobilized Tributylammonium Chloride for the Direct Synthesis of Cyclic Carbonates from Carbon Dioxide and Olefins
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Abstract: An effective direct method for preparing of cyclic carbonates from CO2 and olefins in the presence of tert-butyl hydroperoxide as an oxidant was provided. The first stage, the epoxidation of olefins, was carried out using MoO2(acac)2 as a catalyst (1h, 100 °C), and the second stage, the cycloaddition of CO2 to the resulting epoxide, was proceeded in the presence of immobilized tributylmethylammonium chloride on a polystyrene cross-linked with divinylbenzene, and an aqueous solution of ZnBr2 (100 °C, 0.9?MPa of CO2, 4?h). The proposed method allowed to obtain cyclic carbonates with high yields (50–77%) under mild conditions. Moreover, the immobilized catalyst could be reused at least five times without significant loss of its catalytic activity.
- Siewniak, Agnieszka,Jasiak-Jaroń, Katarzyna,Kotyrba, ?ukasz,Baj, Stefan
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p. 1567 - 1573
(2017/05/16)
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- Synthesis, crystal structures, and catalytic properties of two oxidovanadium(V) complexes with tridentate Schiff bases
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Two new oxidovanadium(V) complexes, [VO2L1] (I) and [VO2L2] (II), where L1 and L2 are the deprotonated forms of 4-methyl-2-[(2-morpholin-4-ylethylimino)methyl]phenol (HL1) and 2-[(2-isopropylaminoethylimino) methyl]-4-trifluoromethoxyphenol (HL2), respectively, have been prepared and characterized by physico chemical methods and single crystal X-ray diffraction (CIF files CCDC nos. 1443671 (I), 1443672 (II)). The V atom in each complex is coordinated by the phenolate oxygen, imino nitrogen and amino nitrogen of the Schiff base ligand, and two oxo groups, forming trigonal-bipyramidal geometry. The oxidation of olefins with the complexes as catalyst was evaluated, which indicated that both complexes showed effective catalytic efficiency in oxidation of several aliphatic and aromatic substrates by using tert-butyl hydrogen peroxide as oxidant.
- Peng
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p. 404 - 410
(2017/06/19)
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- Dipyridylamine molybdenum-oxygen cluster catalyst, as well as preparation method and application thereof
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The invention belongs to the technical field of olefin epoxidation catalyst material preparation, and concretely relates to a preparation method of a dipyridylamine molybdenum-oxygen cluster catalyst and an application thereof. The catalyst can be used for realizing olefin epoxidation, conversion rate reaches 90.8%, and selectivity reaches 89.4%. The catalyst has the advantages of simple preparation raw materials and method.
- -
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Paragraph 0025
(2017/08/29)
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- A dichlorohydrin vapor saponified to produce the epichlorohydrin method
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The invention relates to a method for producing epoxy chloropropane by gas-phase saponification of dichloropropanol. According to the method, after being gasified through a pre-evaporator, dichloropropanol carries carrier particles loaded with alkali to enter an air-lift reactor; generated chloride is loaded on the carrier particles; generated crude epoxy chloropropane gas carrying the carrier particles is subjected to gas-solid separation; gas enters an epoxy chloropropane separation unit; the carrier particles enter the reactor again; a part of loaded alkali in carriers is converted into chloride in the reactor; the carrier particles to be loaded with alkali are replaced; and the replaced carrier particles are repetitively used indiscriminately after being treated. According to the invention, the air-lift reactor is adopted; products and the like are continuously discharged outside the reactor; therefore, the yield can be increased; the carrier particles loaded with alkali are used as reactants; no water is introduced as a solvent; therefore, the process of treating a lot of industrial salt-containing wastewater is omitted; the continuously replaced carrier particles loaded with alkali are regenerated and used indiscriminately; the production cost is reduced; and the continuity and the stability of the reaction process are ensured.
- -
-
Paragraph 0028 - 0030
(2017/06/02)
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- A safer and greener chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate zeolite
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Industrial production of dichloropropanols through chlorohydrination of allyl chloride suffers from a series of disadvantages such as use of hazardous Cl2, low atom economy, low dichloropropanol concentration and serious pollution. In this work, a safer and greener route for chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate (HTS) at mild condition is developed. Unlike the traditional Cl2-based chlorohydrination, this novel method is initiated via synergistic effect of Lewis acidity (HTS) and Br?nsted acidity (HCl) to promote occurrence of oxidation, protonation and nucleophilic reaction of allyl chloride simultaneously and hence dichloropropanols are generated. Owing to a completely different reaction route, the formation of 1,2,3-trichloropropane by-product is depressed and the content of dichloropropanol exceeded 22?wt%, which increase by about 4 times compared with traditional Cl2-based chlorohydrination (the content of dichloropropanol is below 4?wt%). At the optimized conditions, both of the allyl chloride conversion and dichloropropanol selectivity could approach 99% simultaneously and the waste is minimized. What's more, the HTS was reusable. Concentrated HCl solution treatment was adopted to test HTS's stability. The characterization and catalytic evaluation results reveal that, although parts of the framework Ti species have transformed into non-framework Ti and then leached into the solution, HTS remains structural stable, and the allyl chloride conversion and dichloropropanol selectivity didn't decrease obviously during the treatment.
- Peng, Xinxin,Xia, Changjiu,Lin, Min,Shu, Xingtian,Zhu, Bin,Wang, Baorong,Zhang, Yao,Luo, Yibin,Mu, Xuhong
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- Method for continuous preparation of epoxy chloropropane
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The invention relates to a method for continuous preparation of epoxy chloropropane, and is used for mainly solving the problems in the prior art that the utilization rate of raw materials is low and explosion dangers exist because peroxide is easy to decompose when heated. In the presence of a homogeneous molybdenum-based catalyst, epoxy chloropropane is prepared from an organic peroxide and chloropropene. The method includes the following steps: a) a reaction device including n series-connection reaction kettles is provided, wherein n is an integer of more than or equal to 2; b) a material flow A containing fresh chloropropene and a material flow C containing the homogeneous molybdenum-based catalyst are supplied to an inlet of the first reaction kettle; c) a material flow B containing the organic peroxide is divided into n parts for respectively supplying to inlets of the n reaction kettles; and d) a material flow flowing out from an outlet of each the reaction kettle except the last reaction kettle goes into the inlet of the next reaction kettle, and the material flow Vn containing epoxy chloropropane is obtained from an outlet of the last reaction kettle. The method can be used in industrial production of epoxy chloropropane.
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Paragraph 0074-0087
(2017/03/18)
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- Epichlorohydrin preparation method
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The present invention relates to an epichlorohydrin preparation method. A purpose of the present invention is mainly to solve the problems of low raw material utilization rate and explosion risk caused by the easy peroxide decomposition due to heating in the prior art. According to the present invention, in the presence of a homogeneous molybdenum-based catalyst, an organic peroxide and allyl chloride are used to prepare the epichlorohydrin; and the method comprises that: a) a reaction apparatus comprising n reaction kettles connected in series is provided, wherein n is an integer of more than or equal to 2; b) a stream A containing fresh allyl chloride, a stream B containing an organic peroxide and a stream C containing a homogeneous molybdenum-based catalyst are supplied to the inlet of the first reaction kettle; and c) except the last reaction kettle, the streams outflowing from the outlets of each reaction kettle enter the inlets of the next reaction kettles, and the stream Vn containing epichlorohydrin is obtained from the outlet of the last reaction kettle. The method of the present invention can be used in theindustrial epichlorohydrin production.
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Paragraph 0072-0085
(2017/03/18)
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- Continuous epichlorohydrin production method
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The present invention relates to a continuous epichlorohydrin production method. A purpose of the present invention is mainly to solve the problems of low raw material utilization rate and explosion risk caused by the easy peroxide decomposition due to heating in the prior art. According to the present invention, in the presence of a homogeneous molybdenum-based catalyst, an organic peroxide and allyl chloride are used to prepare the epichlorohydrin; the method comprises that: a) a reaction apparatus comprising n reaction kettles connected in series is provided; b) allyl chloride and a catalyst are supplied to the inlet of the first reaction kettle; c) an organic peroxide is divided into n parts, and the n parts are respectively supplied to the inlets of the n reaction kettles; d) except the last reaction kettle, the streams outflowing from the outlets of each reaction kettle enter the inlets of the next reaction kettles, and stream Vn is obtained at the outlet of the last reaction kettle; and e) one part stream Vn' is shunted from the stream Vn, the stream Vn' circulates to the inlet of the first reaction kettle, and the remaining part Vn" is subjected to refining separation so as to obtain the product epichlorohydrin; and the method can be used for the industrial production of the epichlorohydrin.
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Paragraph 0041-0046
(2017/03/21)
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- Production method for epichlorohydrin
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The invention relates to a production method for epichlorohydrin. The method mainly solves the problems of large amounts of waste water and waste residues, serious pollution and strong corrosiveness to equipment in the prior art. A technical scheme of the invention adopts the production method which comprises the following steps: with chloropropene and ethylbenzene hydroperoxide as raw materials and ethylbenzene as a solvent, subjecting the raw materials and a titanium-contained porous silicon dioxide catalyst to contact reaction so as to obtain epichlorohydrin and alpha-methylbenzyl alcohol under the conditions that reaction temperature is 25 to 200 DEG C; reaction absolute pressure is 0.1 to 8.0 MPa; a molar ratio of chloropropene to ethylbenzene hydroperoxide is 1 to 15; and weight-space velocity of ethylbenzene hydroperoxide is 0.01 to 20 h. Thus, the problem is well solved, and the method can be applied in industrial production of epichlorohydrin.
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Paragraph 0068-0069
(2017/03/18)
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- Manganese(II)/Picolinic Acid Catalyst System for Epoxidation of Olefins
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An in situ generated catalyst system based on Mn(CF3SO3)2, picolinic acid, and peracetic acid converts an extensive scope of olefins to their epoxides at 0 °C in 5 min, with remarkable oxidant efficiency and no evidence of radical behavior. Competition experiments indicate an electrophilic active oxidant, proposed to be a high-valent Mn = O species. Ligand exploration suggests a general ligand sphere motif contributes to effective oxidation. The method is underscored by its simplicity and use of inexpensive reagents to quickly access high value-added products.
- Moretti, Ross A.,Du Bois,Stack, T. Daniel P.
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supporting information
p. 2528 - 2531
(2016/07/06)
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- Highly efficient epoxidation of cyclohexene with aqueous H2O2 over powdered anion-resin supported solid catalysts
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Resin supported solid acid catalysts have extended the application of conventional solid acid catalysts in the field of selective oxidations. The present work describes selectively catalytic epoxidation of cyclohexene with aqueous 30% H2O2 over powdered anion-resin supported peroxo phosphotungstic acid heterogeneous catalysts prepared through a simple anion-exchange from powdered chloride-form anion resin without any special pre-exchanged treatment. Among these powdered solid catalysts, anion-exchanged resin D201 supported peroxo phosphotungstic acid exhibits the best activity for the titled reaction to obtain 92.4?mol% conversion and 98.1% selectivity of epoxide, for which D201-PWAR(4) behaves as a truly heterogeneous catalyst. Some factors such as various peroxo phosphotungstic acid concentrations, the oxidants, the solvents, the molar ratios of H2O2/cyclohexene, the catalyst amount, the reaction temperature and time play important roles in controlling the epoxidation.
- Peng,Lu,Ma,Shen,Wei,He,Zhou,Xia
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p. 393 - 399
(2016/08/02)
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- A method for continuously extracting epoxychloropropane
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A chloropropylene oxide continuous extraction method is provided. An extraction system formed by series connection of n extraction devices is adopted for extraction. The n is not less than 2. The method includes: (1) a step of feeding a liquid to be extracted into the extraction system through any one or a plurality of the extraction devices, feeding an extraction agent A from the feeding port of the first extraction device of the extraction system and feeding an extraction agent B from the feeding port of the number n extraction device of the extraction system so that the extraction agents are contacted with the liquid to be extracted, and extracting; and (2) allowing the flow direction of the extraction agent A to be a direction from the first extraction device to the number n extraction device and allowing flow direction of the extraction agent B to be a direction from the number n extraction device to the first extraction device so that extraction raffinate is obtained from the discharging port of the number n extraction device and extract is obtained from the discharging port of the first extraction device. Continuous extraction and separation of the chloropropylene oxide and methanol with high efficiency can be achieved by the method.
- -
-
Paragraph 0064; 0065; 0066
(2017/02/09)
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- Method for synthesizing chloropropylene oxide from glycerin
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The invention discloses a method for synthesizing chloropropylene oxide from glycerin. The method comprises a glycerin chlorination reaction and a dichloropropanol saponification reaction. The method comprises the following steps: carrying out a reaction on glycerin at 105DEG C with adipic acid as a catalyst according to a molar ratio of the catalyst to glycerin of 1:23 to obtain highest-yield dichloropropanol, putting a flask with three necks in an oil bath pot, adding dichloropropanol and sodium hydroxide to the flask according to a molar ratio of sodium hydroxide to dichloropropanol of 1:1-1.4:1, carrying out a cyclization reaction at 40-65DEG C for 20-40min, neutralizing the above obtained reaction product with hydrochloric acid, carrying out water vapor distillation, condensing the obtained mixed steam in order to layer the mixed steam, drying the obtained lower layer liquid with anhydrous sodium chloride overnight, carrying out reduced pressure distillation, and collecting a 83-85DEG C/34000Pa fraction. The method for synthesizing chloropropylene oxide, provided by the invention, has the advantages of short time, high income, few steps, simple requirements of the catalyst, low production cost, energy recycling, reduction of the energy consumption and the material consumption, and improvement of the quality of the product.
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Paragraph 0018
(2017/01/17)
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- Chiral oligomers of spiro-salencobalt(III)X for catalytic asymmetric cycloaddition of epoxides with CO2
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Several new chiral oligomers of spiro-salenCo(III)X (spiro = 1.1′-spirobiindane-7.7′-diol) complexes have been designed, synthesized, and characterized by nuclear magnetic resonance (NMR), infrared (IR), and elemental analyses, in which, the chiral spiro moieties are first introduced into a scaffold of chiral salenCo catalysts. They were used to catalyze the asymmetric cycloaddition of epoxides with carbon dioxide. Under very mild reaction conditions, a kinetic resolution of racemic epoxides with CO2 was smoothly initiated by these chiral oligomer catalysts with good enantioselectivities, which can be attributed to the match effect between chiral backbones of salen and spiro. High stability and easy recyclability are their major advantages.
- Zhu, Zhouhe,Zhang, Yuqian,Wang, Kai,Fu, Xiying,Chen, Fengjuan,Jing, Huanwang
-
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- A continuous preparation dichlorohydrine epoxychloropropane reaction separation coupling process
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The invention relates to a reaction separation coupling technology for continuously preparing epoxy chloropropane from dichloropropanol, belonging to the technical field of the epoxy chloropropane. The technology comprises the steps of enabling the dichloropropanol and an alkali solution to have rapid reaction in a continuous tubular reactor, and then enabling the product to enter a film evaporation device to obtain azeotrope of the epoxy chloropropane and water; finally, carrying out oil-water separation to obtain the epoxy chloropropane. The continuous tubular reactor has a good mixing effect and a heat transfer effect and can accurately control the retention time. The film evaporation is high in evaporation intensity, can accelerate the separation of the azeotrope of the epoxy chloropropane and the water and shortens the retention time of the generated product in a system; the vacuum degree in an evaporator is low, so that the azeotropic point of the product and the water can be reduced, the temperature in the separation process is lower, and the side reaction can be reduced. Compared with the traditional technology, the reaction separation coupling technology for continuously preparing the epoxy chloropropane by the dichloropropanol has the advantages of being short in technological process, short in material retention time, rapid in separation rate, high in device efficiency, low in energy consumption and less in waste water discharge.
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Paragraph 0042
(2017/03/08)
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- Preparation method of epoxy chloropropane and calcium chloride
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The present invention published a preparation method of epoxy chloropropane and calcium chloride. The method uses dichloropropanol hydrochloric acid aqueous solution and calcined quick lime powder as the raw materials, which are subjected to a liquid-solid reaction under the reaction temperature of 15-70 DEG C. The method has the advantages of mild reaction conditions, simple reaction process and easiness to operate; under suitable conditions, the raw material of dichloropropanol can convert completely; the yield of product epoxy chloropropane is up to 99.2%, and the calcium chloride content is 97.0%. The invention uses dichloropropanol hydrochloric acid aqueous solution as the raw material, and adopts quick lime powder as the saponification agent, which is calcined quick lime; and the raw materials are cheap and easily available. The method produces epoxy chloropropane and co-product of calcium chloride with wide scope of application; and the two are easy to be separated, and have strong industrial application value.
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-
Paragraph 0032-0034
(2017/01/26)
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- A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
-
α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
- Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
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p. 420 - 430
(2015/12/31)
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- Engineering the epoxide hydrolase from Agromyces mediolanus for enhanced enantioselectivity and activity in the kinetic resolution of racemic epichlorohydrin
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The biocatalytic production of enantiopure epichlorohydrin (ECH) has been steadily attracting more attention. For industrial applications, it is important to obtain an epoxide hydrolase (EH) that possesses the desired enantioselectivity. Site-saturation and site-directed mutagenesis of the Ser207, Asn240 and Trp182 positions were used to generate variants of EH from Agromyces mediolanus ZJB120203 with enhanced enantioselectivity for the kinetic resolution of racemic ECH. The best variant, VDF (W182F/S207V/N240D), displayed a 7-fold enhanced enantioselectivity toward racemic ECH, with an increase in the enantiomeric ratio value (E value) preferring the (R)-ECH enantiomer from 12.9 of wild-type to 90.0, as well as a 1.7-fold improvement in activity. Furthermore, we successfully applied the created recombinant Escherichia coli whole cells expressing variant VDF in the kinetic resolution of racemic ECH. Enantiopure (S)-ECH could be obtained with an enantiopurity of >99% ee and a yield of 40.5% from 450 mM racemic ECH, which is better than those of other reported EHs. These results demonstrated that the EH obtained in this study could be applied for the efficient resolution of racemic ECH.
- Xue, Feng,Liu, Zhi-Qiang,Wan, Nan-Wei,Zhu, Hang-Qin,Zheng, Yu-Guo
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p. 31525 - 31532
(2015/04/22)
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- A One-Step Biocatalytic Process for (S)-4-Chloro-3-hydroxybutyronitrile using Halohydrin Dehalogenase: A Chiral Building Block for Atorvastatin
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(S)-4-Chloro-3-hydroxybutyronitrile [(S)-CHBN] was used as a chiral building block for the preparation of atorvastatin. In this study, (R,S)-epichlorohydrin [(R,S)-ECH] and 1,3-dichloro-2-propanol (1,3-DCP) were investigated to prepare (S)-CHBN by using the halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1. Preparing (S)-CHBN from (R,S)-ECH gave a modest enantiomeric excess (ee), whereas by using 1,3-DCP as the substrate, (S)-CHBN was obtained with 97.3 % ee after pH optimization. However, a low ee value and low yield of (S)-CHBN were obtained if the substrate concentration was increased to 10 g L-1. To obtain a higher ee value and yield, 16 mutants were constructed and screened. The variant W249F with improvements in activity and enantioselectivity was identified and applied at a 1,3-DCP loading of 10 g L-1, which gave (S)-CHBN in 86 % yield with 97.5 % ee in 1 h. This is the first report of a one-step biocatalytic process for the preparation of (S)-CHBN from prochiral 1,3-DCP.
- Wan, Nan-Wei,Liu, Zhi-Qiang,Xue, Feng,Shen, Zhen-Yang,Zheng, Yu-Guo
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p. 2446 - 2450
(2015/08/24)
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- Dinuclear salen cobalt complex incorporating Y(OTf)3: enhanced enantioselectivity in the hydrolytic kinetic resolution of epoxides
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The activation of inactive Jacobsen's chiral salen Co(ii) (salen = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) compound is attained by dinuclear chiral salen Co(iii)-OTf complex formation with yttrium triflate. The yttrium metal not only displays a promoting effect on electron transfer, but also assists in forming two stereocentres of a Lewis acid complex with Co(iii)-OTf. We found that the binuclear Co-complex significantly enhanced reactivity and enantioselectivity in the hydrolytic kinetic resolution of terminal epoxides compared to its analogous monomer and kinetic data are also consistent with these results.
- Patel, Deepak,Kurrey, Ganesh Ram,Shinde, Sandip S.,Kumar, Pradeep,Kim, Geon-Joong,Thakur, Santosh Singh
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p. 82699 - 82703
(2015/10/19)
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- Efficient synthesis of (S)-epichlorohydrin in high yield by cascade biocatalysis with halohydrin dehalogenase and epoxide hydrolase mutants
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Enantioselective biotransformation of prochiral 1,3-DCP by halohydrin dehalogenases (HHDHs) is particularly attractive since 100% yield of chiral epichlorohydrin (ECH) may be obtained. HheC mutant (P175S/W249P) displayed greatly improved enantiomeric excess (ee) of (S)-ECH from 5% to 95.3% in the catalyzed dehalogenation of 1,3-DCP at pH 8.0. (S)-ECH was enantioselectively biotransformed from 40 mM 1,3-DCP with 92.3% ee and 93.2% yield at pH 10.0. To increase the ee of (S)-ECH, the catalysis was carried out using HheC mutant coupled with epoxide hydrolase mutant and the maximum yield and ee of (S)-ECH reached 91.2% and > 99%.
- Xue, Feng,Liu, Zhi-Qiang,Wang, Ya-Jun,Zhu, Hang-Qin,Wan, Nan-Wei,Zheng, Yu-Guo
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p. 147 - 149
(2015/10/19)
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