- Determining Roles of Cu0 in the Chemosynthesis of Diols via Condensed Diester Hydrogenation on Cu/SiO2 Catalyst
-
Copper-based catalyst was applied in the condensed diester hydrogenation with unexpected high selectivity (～100 percent) to 1,6-hexanediol. On basis of the mass transfer analysis and kinetics results, the reaction rate of the condensed diester hydrogenation was deduced to be controlled by the activation of hydrogen on Cu0 sites, which was further demonstrated by the correlations between the catalytic activity and different copper species. Importantly, this catalysis mechanism is different with that of gas-phase diester hydrogenation, which is generally determined by the adsorption of ester on Cu+ species.
- Wang, Weichao,Wang, Hui,Zhang, Jingwei,Kong, Lingxin,Huang, Huijiang,Liu, Wei,Wang, Shengping,Ma, Xinbin,Zhao, Yujun
-
-
Read Online
- CuZn Catalysts Superior to Adkins Catalysts for Dimethyl Adipate Hydrogenolysis
-
Industrial hydrogenolysis of esters to alcohols relies on the use of Adkins catalysts whose production and disposal is an environmental burden. This work is focused on CuZn catalysts that represent an ecological alternative to Adkins catalysts. Four CuZn catalysts with Cu/Zn atomic ratio ranging from 0.5 to 2.0 and single phase CuO and ZnO catalysts were prepared by co-precipitation and their hydrogenolysis activity was compared with a commercial Adkins catalyst. Dimethyl adipate was used to test the catalyst performance in a flow reactor at temperatures ranging from 175 to 205 °C and hydrogen pressure of 16 MPa. The increase in ZnO content was directly responsible for the reduction in copper crystallite size and increase in the catalyst specific surface area. The CuZn catalysts exhibited higher conversion than the Adkins catalyst despite their specific surface area declined during the experiments more significantly than that of the Adkins catalyst. Nonetheless, the TOF of CuZn catalysts exceeded that of the commercial Adkins catalyst.
- Pospelova, Violetta,Aubrecht, Jaroslav,Kikhtyanin, Oleg,Pacultová, Kate?ina,Kubi?ka, David
-
-
Read Online
- On the selective acid-catalysed dehydration of 1,2,6-hexanetriol
-
Selectivity results for the dehydration of 1,2,6-hexanetriol over solid acid catalysts are reported. A slate of catalysts including zeolites, amorphous silica-alumina, and niobias were tested and the selectivity towards either cyclic ethers or α,ω-dioxygenates was found to be mildly correlated with the acid strength of the fresh catalyst. In general, a ring closing dehydration reaction to a pyran was the dominant reaction pathway. Differences in the catalysts were mitigated by significant coke formation.
- Nolan, Michael R.,Sun, Geng,Shanks, Brent H.
-
-
Read Online
- Synthesis of Supported RhMo and PtMo Bimetallic Catalysts by Controlled Surface Reactions
-
We previously described a synthesis method to prepare bimetallic catalysts with narrow nanoparticle size and composition distributions by means of controlled surface reactions (CSR) between a reduced supported metal nanoparticle and an organometallic precursor of an oxophilic promoter metal. Herein, we report a comparison of such catalysts with those prepared by traditional incipient wetness impregnation. STEM/EDS analysis indicates that catalysts prepared by CSR exhibit more effective interaction of metals, thereby minimizing the undesirable formation of component-rich nanoparticles and/or monometallic domains. Reaction kinetics studies using these bimetallic catalysts reveal that optimal conversion rates in a selective CO hydrogenolysis reaction (i.e., hydrogenolysis of 2-(hydroxymethyl)tetrahydropyran to 1,6-hexanediol) could be achieved using a lower amount of the oxophilic promoter metal for the catalysts prepared by the CSR approach, as compared to their impregnated counterparts. A superior method for greater results: At the same conversion rate level, catalysts prepared by controlled surface reactions (CSR) requires smaller amount of promoter as compared to those prepared by incipient wetness impregnation (IWI). This increased performance is attributed to the uniform bimetallic composition of the catalysts prepared by CSR.
- Alba-Rubio, Ana C.,Sener, Canan,Hakim, Sikander H.,Gostanian, Thomas M.,Dumesic, James A.
-
-
Read Online
- Ti3+ Tuning the Ratio of Cu+/Cu0 in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction
-
Hydrogenation of diesters to diols is a vital process for chemical industry. The inexpensive Cu+/Cu0-based catalysts are highly active for the hydrogenation of esters, however, how to efficiently tune the ratio of Cu+/Cu0 and stabilize the Cu+ is a great challenge. In this work, it is demonstrated that doped Ti ions can tune the ratio of Cu+/Cu0 and stabilize the Cu+ by the Ti-O-Cu bonds in Ti-doped SiO2 supported Cu nanoparticle (Cu/Ti–SiO2) catalysts for the high conversion of dimethyl adipate to 1,6-hexanediol. In the synthesis of the catalysts, the Ti4+-O-Cu2+ bonds promote the reduction of Cu2+ to Cu+ by forming Ti3+-OV-Cu+ (OV: oxygen vacancy) bonds and the amount of Ti doping can tune the ratio of Cu+/Cu0. In the catalytic reaction, the O vacancy activates C=O in the ester by forming new Ti3+δ-OR-Cu1+δ bonds (OR: reactant oxygen), and Cu0 activates hydrogen. After the products are desorbed, the Ti3+δ-OR-Cu1+δ bonds return to the initial state of Ti3+-OV-Cu+ bonds. The reversible Ti-O-Cu bonds greatly improve the activity and stability of the Cu/Ti–SiO2 catalysts. When the content of Ti is controlled at 0.4?wt%, the conversion and selectivity can reach 100% and 98.8%, respectively, and remain stable for 260 h without performance degradation.
- Zhang, Ziyang,Wang, Zhong-Li,An, Kang,Wang, Jiaming,Zhang, Siran,Song, Pengfei,Bando, Yoshio,Yamauchi, Yusuke,Liu, Yuan
-
-
Read Online
- Reductive depolymerization of polyesters and polycarbonates with hydroboranes by using a lanthanum(iii) tris(amide) catalyst
-
The homogeneous reductive depolymerization of polyesters and polycarbonates with hydroboranes is achieved with the use of an f-metal complex catalyst. These polymeric materials are transformed into their value-added alcohol equivalents. Catalysis proceeds readily, under mild conditions, with La[N(SiMe3)2]3 (1 mol%) and pinacolborane (HBpin) and shows high selectivity towards alcohols and diols, after hydrolysis.
- Berthet, Jean-Claude,Cantat, Thibault,Kobylarski, Marie
-
supporting information
p. 2830 - 2833
(2022/03/09)
-
- Understanding of the key properties of supported Cu-based catalysts and their influence on ester hydrogenolysis
-
The application of Cr-free Cu-based catalysts in ester hydrogenolysis is a modern environmentally-friendly research approach. The comprehensive study of four supported Cu-based catalysts was performed using 8 wt% of Cu loaded on Al2O3, ZnO, TiO2 and ZrO2 supports by an impregnation method. Using XRD, H2-TPR, BET, pyridine-TPD, CO2-TPD and N2O-RFC methods, the effect of the support on the formation of Cu-nanoparticles was described. Al2O3 was evaluated as the support ensuring the highest nanoparticles dispersion, while Cu nanoparticles in Cu-TiO2 were liable to sintering. The catalysts were tested in dimethyl adipate hydrogenolysis, where the catalyst performance and activity (TOF) were evaluated and Cu-ZrO2 showed the best results. A correlation between the number of acid-base sites and the catalyst selectivity was revealed and the catalyst effect on the formation of various by-products was described. The intrinsic selectivity to hydrogenolysis products was found to decrease with the increasing acid-base character of the supports whereas the selectivity to transesterification and cyclization products increased. The hydrogenolysis activity was not a simple function of the number of the surface copper atoms, but it was affected by the support nature and its properties.
- Aubrecht, Jaroslav,Kikhtyanin, Oleg,Kubi?ka, David,Lhotka, Miloslav,Pospelova, Violetta
-
-
- MOF-derived hcp-Co nanoparticles encapsulated in ultrathin graphene for carboxylic acids hydrogenation to alcohols
-
Highly efficient conversion of carboxylic acids to valuable alcohols is a great challenge for easily corroded non-noble metal catalysts. Here, a series of few-layer graphene encapsulated metastable hexagonal closed-packed (hcp) Co nanoparticles were fabricated by reductive pyrolysis of metal-organic framework precursor. The sample pyrolyzed at 400 °C (hcp-Co@G400) presented outstanding performance and stability for converting a variety of functional carboxylic acids and its turnover frequency was one magnitude higher than that of conventional facc-centered cubic (fcc) Co catalysts. In situ DRIFTS spectroscopy of model reaction acetic acid hydrogenation and DFT calculation results confirm that carboxylic acid initially undergoes dehydroxylation to RCH2CO* followed by consecutive hydrogenation to RCH2CH2OH through RCH2COH*. Acetic acid prefers to vertically adsorb at hcp-Co (0 0 2) facet with a much lower adsorption energy than parallel adsorption at fcc-Co (1 1 1) surface, which plays a key role in decreasing the activation barrier of the rate-determining step of acetic acid dehydroxylation.
- Dong, Mei,Fan, Weibin,Gao, Xiaoqing,Zhu, Shanhui
-
p. 201 - 211
(2021/06/03)
-
- Method for preparing 1, 5-pentanediol or 1, 6-hexanediol from bio-based furan compound
-
The invention discloses a method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing a bio-based furan compound, which comprises the following steps of: reacting the bio-based furan compound serving as a raw material for 1-48 hours in a proper solvent under the conditions of pressure of 0.5-10 MPa and temperature of 20-200 DEG C in a reducing gas atmosphere under the action of a catalyst, separating the catalyst, and distilling out the solvent to obtain the target product 1,5-pentanediol or 1, 6-hexanediol. According to the method disclosed by the invention, efficient conversion of the bio-based furan compound is realized under relatively mild and environment-friendly conditions by utilizing chemically synthesized renewable resource bio-based furan, and the produced 1, 5-pentanediol or 1, 6-hexanediol is a polymer monomer, so that the application range of the bio-based furan compound is expanded, the comprehensive utilization of the straws is further promoted, and carbon neutralization is promoted.
- -
-
Paragraph 0006; 0021
(2021/06/26)
-
- Method for preparing 1, 6-hexamethylenediamine from 5-hydroxymethylfurfural
-
The invention relates to a method for preparing 1, 6-hexamethylenediamine from 5-hydroxymethylfurfural, which is characterized in that the 5-hydroxymethylfurfural is used as a raw material, and the 1, 6-hexamethylenediamine is synthesized by a two-step method under the action of a catalyst. The method comprises the following steps: 1) in a hydrogen atmosphere, reacting the raw material 5-hydroxymethylfurfural with ammonia in the presence of a reductive amination catalyst to generate 2, 5-dimethylamine tetrahydrofuran; and 2) continuing the reaction, and carrying out a ring-opening reaction on the hydrodeoxygenation catalyst to produce the target product 1, 6-hexamethylenediamine. The method is characterized in that the reductive amination catalyst in the step 1) is an M1-M2 supported multi-metal component catalyst. The method is characterized in that the hydrodeoxygenation catalyst in the step 2) is a supported catalyst, and the metal active component is selected from one or more of transition metal elements Rh, Re, Pt, Ir, Pd and Ru. The 1, 6-hexamethylenediamine is produced by using the bio-based material monomer 5-hydroxymethylfurfural as the raw material, so that the method is green and clean, the process is easy to operate, the yield is high, and a wide application prospect is provided for biomass conversion.
- -
-
Paragraph 0140; 0146-0147
(2021/06/06)
-
- Towards efficient Cu/ZnO catalysts for ester hydrogenolysis: The role of synthesis method
-
Cu/ZnO catalysts represent an environmentally friendly alternative to Adkins catalysts used for ester hydrogenolysis. Cu/ZnO are mostly synthesized by co-precipitation (COP); however, other synthesis methods may help to obtain small highly dispersed Cu crystallites advantageous for catalyst activity. A comparative study on the effect of synthesis method on Cu/ZnO catalysts properties and activity is missing. Thus, we synthesized 8 wt% Cu/ZnO catalysts by five methods (COP, deposition-precipitation (DP), chemisorption-hydrolysis (CH), incipient wetness (IWI) and wet impregnation (WI)), characterized and tested them in dimethyl adipate hydrogenolysis. The CH-prepared catalyst was prone to Cu sintering, which impaired its performance. IWI led to large Cu nanoparticles, pore blocking and poor catalytic performance. COP and DP resulted in the smallest Cu nanoparticles (13?14 nm), largest Cu surface area (3.9–4.2 m2 gcat?1) and specific surface area (40?43 m2 gcat?1) reflected in their superior catalytic activity making DP a good alternative to COP to prepare active Cu/ZnO catalysts.
- Aubrecht, Jaroslav,Kikhtyanin, Oleg,Kubi?ka, David,Pospelova, Violetta
-
-
- Interworking ligand, hydroformylation catalyst and preparation method of dihydric alcohol
-
The invention discloses an interworking ligand, a hydroformylation catalyst and a preparation method of dihydric alcohol. The interworking ligand comprises a ligand unit I and a ligand unit II, has the characteristics of a bidentate phosphine ligand, and is high in catalytic activity and good in stability; and when the catalyst is used for preparing dihydric alcohol from olefin, linear alcohol can be obtained through a one-step method, and the content of by-products in a traditional series process is reduced. The method has the advantages of simple and convenient process, low cost and energy consumption, good production safety, high product quality and the like, and is particularly suitable for large-scale industrial production.
- -
-
Paragraph 0071; 0079-0080
(2021/07/09)
-
- Depolymerization of Technical-Grade Polyamide 66 and Polyurethane Materials through Hydrogenation
-
Chemical recycling provides a promising solution to utilize plastic waste. Here, a catalytic hydrogenative depolymerization of polyamide 66 (PA 66) and polyurethane (PU) was developed. The system employed Ru pincer complexes at high temperature (200 °C) in THF solution, and even technical-grade polymers could be hydrogenated with satisfactory yields under these conditions. A comparison of the system with some known heterogeneous catalysts as well as catalyst poisoning tests supported the homogeneity of the system. These results demonstrate the potential of chemical recycling to regain building blocks for polymers and will be interesting for the further development of polymer hydrogenation.
- Zhou, Wei,Neumann, Paul,Al Batal, Mona,Rominger, Frank,Hashmi, A. Stephen K.,Schaub, Thomas
-
p. 4176 - 4180
(2020/11/30)
-
- Synthetic method of linear dihydric alcohol
-
The invention discloses a synthetic method of linear dihydric alcohol. The synthetic method comprises the following steps: (1) carrying out hydrosilylation reaction on alpha-olefin and siloxane to obtain alkyl siloxane; (2) carrying out hydroxymethylation reaction on alkyl siloxane, organic metal alkali and a hydrogen acceptor to obtain silyl alcohol; and (3) carrying out oxidation reaction on the silyl alcohol, fluorine-containing metal salt and peroxide to obtain the linear dihydric alcohol. The method has the advantages of mild process, easily available raw material sources, no need of post-treatment after the reaction is completed, capability of being directly used for the next reaction, simplification of the process flow, high conversion rate, high selectivity, low cost and suitability for large-scale production.
- -
-
Paragraph 0118-0119; 0122
(2021/09/01)
-
- Dinuclear copper catalyst for the oxidation/oxygenation of hydrocarbons
-
The subject invention provides synthetic compounds, and compound complexes having catalytic activities towards oxidation or oxygenation, and/or dehydrogenation of various substrates comprising C—H bonds. The catalysts of the subject invention comprise a d
- -
-
Page/Page column 23
(2021/12/02)
-
- Hydrosilylation of Esters Catalyzed by Bisphosphine Manganese(I) Complex: Selective Transformation of Esters to Alcohols
-
Selective and efficient hydrosilylations of esters to alcohols by a well-defined manganese(I) complex with a commercially available bisphosphine ligand are described. These reactions are easy alternatives for stoichiometric hydride reduction or hydrogenation, and employing cheap, abundant, and nonprecious metal is attractive. The hydrosilylations were performed at 100 °C under solvent-free conditions with low catalyst loading. A large variety of aromatic, aliphatic, and cyclic esters bearing different functional groups were selectively converted into the corresponding alcohols in good yields.
- Bagh, Bidraha,Behera, Rakesh R.,Ghosh, Rahul,Khamari, Subrat,Panda, Surajit
-
supporting information
p. 3642 - 3648
(2020/04/20)
-
- Cobalt-catalysed selective synthesis of aldehydes and alcohols from esters
-
Efficient and selective reduction of esters to aldehydes and alcohols is reported in which a simple cobalt pincer catalyst catalyses both transformations using diethylsilane as a reductant. Remarkably, the reaction selectivity is controlled by the stoichiometry of diethylsilane. This journal is
- Pattanaik, Sandip,Gunanathan, Chidambaram
-
supporting information
p. 7345 - 7348
(2020/07/14)
-
- METHOD FOR PRODUCING ALCOHOL
-
PROBLEM TO BE SOLVED: To provide a method for producing selectively alcohol from carboxylic acid under mild conditions. SOLUTION: In the presence of a catalyst with M1 and M2 as metal species supported on a support, a substrate is reduced to produce a corresponding alcohol. (M1 is Rh, Pt, Ru, Ir, or Pd; M2 is Sn, V, Mo, W, or Re; the support is ZrO2, hydroxyapatite, Nb2O5, fluoroapatite, or hydrotalcite; the substrate is the formula 1a, 1b, or 1c). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPO&INPIT
- -
-
Paragraph 0101-0110
(2020/11/26)
-
- Fixed bed reaction process for directly preparing 1,6-hexanediol from 1,6-adipic acid
-
The invention relates to a fixed bed reaction process for directly preparing 1,6-hexanediol from 1,6-adipic acid, wherein the process comprises the following steps: (1) respectively adding the raw material 1,6-adipic acid and a solvent into a mixing tank, and at the same time, heating the mixing tank; (2) uniformly mixing the raw material solution prepared in the step (1) with hydrogen and feedingthe mixture into a fixed bed reactor filled with supported ruthenium and rhodium catalysts according to a certain air speed by a pump, and carrying out reduction reaction; and (4) enabling the reactant obtained in the step (3) to pass through a condenser, and carrying out gas-liquid separation to obtain the 1,6-hexanediol product. The supported ruthenium and rhodium catalysts are innovatively adopted, a catalyst carrier is aluminum oxide, adipic acid is used as a raw material, and 1,6-hexanediol is continuously prepared by the fixed bed reactor. The reaction steps are simple, the product conversion rate and selectivity are high, and the application prospect is good.
- -
-
Paragraph 0022-0037
(2020/04/17)
-
- Reaction process for preparing 1,6-hexanediol by reducing 1,6-adipic acid
-
The invention provides a reaction process for preparing 1,6-hexanediol by reducing 1,6-adipic acid. The process comprises the following steps of (1), adding the raw material 1,6-adipic acid and waterinto a mixing tank according to a certain ratio, and performing stirring, heating and dissolving; (2), feeding raw material liquid prepared in the step (1) into a gas-liquid mixer by using a pump according to a certain space velocity, uniformly mixing the raw material liquid with hydrogen, and keeping the temperature; (3), uniformly feeding a mixed raw material into a fixed bed reactor filled witha Ni/Rh/Al2O3 catalyst, and carrying out a hydrogenation reduction reaction; and (4), enabling a reactant obtained in the step (3) to pass through a condenser, and carrying out gas-liquid separationto obtain the 1,6-hexanediol product. Nickel is used as a main catalyst, so that the cost of the catalyst is reduced under the condition of not reducing the reaction performance; and meanwhile, the 1,6-hexanediol is prepared through continuous reduction by utilizing a fixed bed reaction process, and the reaction process is simple and easy to industrialize.
- -
-
Paragraph 0021-0023; 0024-0026; 0027-0029; 0030-0047
(2020/12/08)
-
- One-pot biosynthesis of 1,6-hexanediol from cyclohexane by: De novo designed cascade biocatalysis
-
1,6-Hexanediol (HDO) is an important precursor in the polymer industry. The current industrial route to produce HDO involves energy intensive and hazardous multistage (four-pot-four-step) chemical reactions using cyclohexane (CH) as the starting material, which leads to serious environmental problems. Here, we report the development of a biocatalytic cascade process for the biotransformation of CH to HDO under mild conditions in a one-pot-one-step manner. This cascade biocatalysis operates by using a microbial consortium composed of three E. coli cell modules, each containing the necessary enzymes. The cell modules with assigned functions were engineered in parallel, followed by combination to construct E. coli consortia for use in biotransformations. The engineered E. coli consortia, which contained the corresponding cell modules, efficiently converted not only CH or cyclohexanol to HDO, but also other cycloalkanes or cycloalkanols to related dihydric alcohols. In conclusion, the newly developed biocatalytic process provides a promising alternative to the current industrial process for manufacturing HDO and related dihydric alcohols. This journal is
- Kang, Lixin,Li, Aitao,Li, Qian,Li, Renjie,Wang, Fei,Yu, Xiaojuan,Zhang, Zhongwei,Zhao, Jing
-
p. 7476 - 7483
(2020/11/23)
-
- Nickel-Catalyzed Formal Aminocarbonylation of Unactivated Alkyl Iodides with Isocyanides
-
Herein, we disclose a Ni-catalyzed formal aminocarbonylation of primary and secondary unactivated aliphatic iodides with isocyanides to afford alkyl amide, which proceeds via the selective monomigratory insertion of isocyanides with alkyl iodides, subsequent β-hydride elimination, and hydrolysis process. The reaction features wide functional group tolerance under mild conditions. Additionally, the selective, one-pot hydrolysis of reaction mixture under acid conditions allows for expedient synthesis of the corresponding alkyl carboxylic acid.
- Chen, Yifeng,Huang, Wenyi,Qu, Jingping,Shrestha, Mohini,Wang, Yun,Weng, Yangyang
-
supporting information
p. 3245 - 3250
(2020/04/21)
-
- Hydrogenation of adipic acid to 1,6-hexanediol by supported bimetallic Ir-Re catalyst
-
A series of supported Ir-Re catalysts have been synthesized and used for the hydrogenation of adipic acid to 1,6-hexanediol. The influences of supporting materials and the Ir/Re atomic ratio on the catalytic performances have been studied. Results suggested that Ir-Re supported on carbon materials and alumina had appropriate acid sites and better activity for the hydrogenation of adipic acid. Compared to the monometallic catalysts, synergistic interaction was generated and electrons were delivered from Ir to Re. The uniform distribution of metal particles in the Ir-Re catalysts and the well restrained H2-spillover effect facilitated the transformation of adipic acid and the selective production of 1,6-hexanediol. The selectivity of 1,6-hexanediol was 59% with complete conversion of adipic acid at 180 °C in 10 MPa H2 after reaction for 16 h. After four times of reaction, the selectivity of 1,6-hexanediol only decreased about 4%.
- Li, Xiaoyue,Liang, Changhai,Luo, Jingjie
-
-
- Catalytic Hydrogenation of Thioesters, Thiocarbamates, and Thioamides
-
Direct hydrogenation of thioesters with H2 provides a facile and waste-free method to access alcohols and thiols. However, no report of this reaction is documented, possibly because of the incompatibility of the generated thiol with typical hydrogenation catalysts. Here, we report an efficient and selective hydrogenation of thioesters. The reaction is catalyzed by an acridine-based ruthenium complex without additives. Various thioesters were fully hydrogenated to the corresponding alcohols and thiols with excellent tolerance for amide, ester, and carboxylic acid groups. Thiocarbamates and thioamides also undergo hydrogenation under similar conditions, substantially extending the application of hydrogenation of organosulfur compounds.
- Luo, Jie,Rauch, Michael,Avram, Liat,Ben-David, Yehoshoa,Milstein, David
-
supporting information
p. 21628 - 21633
(2021/01/11)
-
- Base-Free Iron Catalyzed Transfer Hydrogenation of Esters Using EtOH as Hydrogen Source
-
Herein, we report on the use of the iron pincer complex Iron-MACHO-BH, in the base-free transfer hydrogenation of esters with EtOH as a hydrogen source. More than 20 substrates including aromatic and aliphatic esters and lactones were reduced affording the desired primary alcohols and diols with moderate to excellent isolated yields. It is also possible to reduce polyesters to the diols with this method, enabling a novel way of plastic recycling. Reduction of the renewable substrate methyl levulinate proceeds to form 1,4-pentanediol directly. The yields are largely governed by the equilibrium between the alcohol and the ethyl ester.
- Farrar-Tobar, Ronald A.,Wozniak, Bartosz,Savini, Arianna,Hinze, Sandra,Tin, Sergey,de Vries, Johannes G.
-
supporting information
p. 1129 - 1133
(2019/01/04)
-
- Synthesis technology for 1,6-hexanediol
-
The invention relates to the technical field of organic compound preparation, and concretely discloses a synthesis technology for 1,6-hexanediol. The technology comprises the following steps: synthesis of a raw material dimethyl adipate, preparation of a reaction solution, introduction of hydrogen to a hydrogenation reaction device for evacuation, catalyst reduction, reacting of the reaction solution, and rectification of the prepared hexanediol. The technology has the characteristics of few steps, simplicity and convenience in operation, and safeness; a Cu-Co-Ni catalyst adopted in the invention has the characteristics of long service period, stability in reaction, and safeness; the synthesis technology allows the conversion rate of the dimethyl adipate to be 99.6% or more and close to 100%, the selectivity of the hexanediol to be 97% or more and the purity of the rectified hexanediol to be 98.7% or more; and excess methanol used in the present invention can be recovered, so the production cost is reduced, and the environmental problems of post-treatment is solved, thereby the technology has certain market competitiveness.
- -
-
Paragraph 0027; 0031-0041; 0045-0055; 0059-0068
(2019/09/13)
-
- General and Phosphine-Free Cobalt-Catalyzed Hydrogenation of Esters to Alcohols
-
Catalytic hydrogenation of esters is essential for the sustainable production of alcohols in organic synthesis and chemical industry. Herein, we describe the first non-noble metal catalytic system that enables an efficient hydrogenation of non-activated esters to alcohols in the absence of phosphine ligands (with a maximum turnover number of 2391). The general applicability of this protocol was demonstrated by the high-yielding hydrogenation of 39 ester substrates including aromatic/aliphatic esters, lactones, polyesters and various pharmaceutical molecules.
- Shao, Zhihui,Zhong, Rui,Ferraccioli, Raffaella,Li, Yibiao,Liu, Qiang
-
supporting information
p. 1125 - 1130
(2019/10/22)
-
- METHOD FOR PRODUCING ε-CAPROLACTONE
-
A method for manufacturing andepsi;-caprolactone of the present invention comprises steps of converting adipic acid to 1,6-hexanediol and ring-closing 1,6-hexanediol to andepsi;-caprolactone. The method for manufacturing andepsi;-caprolactone of the present invention comprises steps of: converting adipic acid to 1,6-hexanediol; partially oxidizing the 1,6-hexanediol to 6-hydroxycaproic acid; and ring-closing 6-hydroxycaproic acid into andepsi;-caprolactone. The present process provides a novel approach for the synthesis of andepsi;-caprolactone with a high yield and selectivity.COPYRIGHT KIPO 2020
- -
-
Paragraph 0075-0077
(2020/03/04)
-
- N-butyl lithium based fatty alcohol preparation method
-
The invention relates to an n-butyl lithium based fatty alcohol preparation method. In an inert gas atmosphere, borane and aliphatic carboxylic acid are mixed, then n-butyl lithium taken as the catalyst is added to carry out hydroboration reactions; and after the hydroboration reactions, silica gel and methanol are added to carry out hydrolysis reactions to obtain the fatty alcohols. N-butyl lithium can efficiently catalyze the hydroboration reactions between carboxylic acids and borane at a room temperature, the used catalyst only accounts for 0.2 mol% of the carboxylic acids, compared with aconventional catalyst system, a commercial catalyst namely n-butyl lithium is adopted, the reaction conditions are mild, and the yield of fatty alcohols with different substitutes under restricted conditions is high.
- -
-
-
- Interface synergy between IrOx and H-ZSM-5 in selective C–O hydrogenolysis of glycerol toward 1,3-propanediol
-
Site-selective deoxygenation of hydroxyl groups represents essential processes to access valuable functionalized bio-based compounds with industrial potential. One of the challenging tasks in this context is to convert biodiesel-derived glycerol in the presence of abundant water directly to 1,3-propanediol (1,3-PDO), a key component of the emerging polymer industry. Herein, a monometallic iridium supported on H-ZSM-5 in the absence of Re oxophilic metal oxides was prepared via grinding-assisted impregnation procedures and attempted as an effective and recyclable catalyst for the aqueous-phase selective hydrogenolysis of glycerol toward 1,3-PDO in the absence of acid additives. The results revealed the necessity to control the Ir domain dispersions, Ir0/Ir3+ ratio and the amounts of overall acid/Br?nsted acid sites. Activity depended linearly on the amount of overall and Br?nsted acid sites, and 1,3-PDO selectivity increased in the presence of Ir-induced Br?nsted acid sites, denoted as Ir-O(H)-H-ZSM-5. We speculate that Ir-O(H)-H-ZSM-5 are generated by the interfacial synergistic interaction between IrOx and H-ZSM-5 through hydrogen spillover and reverse hydrogen spillover according to the reported literatures. The reaction mechanism to elucidate the role of Ir-O(H)-H-ZSM-5 sites in glycerol hydrogenolysis was also postulated based on extensive characterization and catalytic reaction results.
- Wan, Xiaoyue,Zhang, Qi,Zhu, Mingming,Zhao, Yi,Liu, Yongmei,Zhou, Chunmei,Yang, Yanhui,Cao, Yong
-
p. 339 - 350
(2019/07/03)
-
- Diaminodiphosphine tetradentate ligand and ruthenium complex thereof, and preparation methods and applications of ligand and complex
-
The invention discloses a diaminodiphosphine tetradentate ligand and a ruthenium complex thereof, and preparation methods and applications of the ligand and the complex, and provides a ruthenium complex represented by a formula I, wherein L is a diaminodiphosphine tetradentate ligand represented by a formula II, and X and Y are respectively and independently chlorine ion, bromine ion, iodine ion,hydrogen negative ion or BH4. According to the present invention, the ruthenium complex exhibits excellent catalytic activity in the catalytic hydrogenation reactions of ester compounds, has high yield and high chemical selectivity, is compatible with conjugated and non-conjugated carbon-carbon double bond, carbon-carbon triple bond, epoxy, halogen, carbonyl and other functional groups, and hasgreat application prospects.
- -
-
Paragraph 0301-0303; 0305
(2019/11/04)
-
- Borohydride reduction stabilizing system and method for reducing ester into alcohol
-
The invention provides a borohydride reduction stabilizing system and a method for reducing ester into alcohol. The borohydride reduction stabilizing system comprises a borohydride reducing agent anda stabilizer for stabilizing the borohydride reducing agent, wherein the borohydride reducing agent is sodium borohydride or potassium borohydride, and the stabilizer is an alkali metal salt of alcohol. On the basis of an existing sodium borohydride/potassium reducing agent, an alcohol alkali metal salt (such as sodium alcoholate or potassium alcoholate) is added, and then the sodium borohydride/potassium reducing agent can keep stable and is not decomposed under a heating condition, so that on one hand, reduction activity is maintained in a relatively high state and the situation of excessiveuse is reduced, and on the other hand, generation of hydrogen is reduced and the process risk is reduced.
- -
-
Paragraph 0131; 0132; 0133
(2019/09/13)
-
- Ruthenium complexes with N-functionalized secondary amino ligands: a new class of catalysts toward efficient hydrogenation of esters
-
A series of ruthenium complexes (o-PPh2C6H4NHR)2RuCl2 (R = Me, 3; Et, 4; CH2Ph, 5) and (o-PPh2C6H4NH2)[(CH2NHR)2]RuCl2 (R = Me, 7; Et, 8; iPr, 9) modulated with mono-N-functionalized secondary amino ligands were synthesized and demonstrated as efficient catalysts in the hydrogenation of esters into alcohols. The catalytic performances of these new complexes are much better than their corresponding primary amino ligand-constituted complexes (o-PPh2C6H4NH2)2RuCl2 (2) and (o-PPh2C6H4NH2)[(CH2NH2)2]RuCl2 (6). The significant improvement is attributed to the increased electron density of the secondary amino ligand in comparison with that of the primary amino ligand.
- Fang, Xiaolong,Li, Bin,Zheng, Jianwei,Wang, Xiaoping,Zhu, Hongping,Yuan, Youzhu
-
supporting information
p. 2290 - 2294
(2019/02/19)
-
- The reductive deaminative conversion of nitriles to alcohols using: Para -formaldehyde in aqueous solution
-
We report herein, for the first time, the application of para-formaldehyde (pFA) to the reductive deamination of both aliphatic and aromatic nitriles in aqueous solution under transfer hydrogenation conditions. A broad range of primary alcohols have been synthesized selectively with very good to excellent yields under the optimized conditions. The study disclosed that the air-stable, inexpensive and commercially available catalyst [Ru(p-cymene)Cl2]2 acts as the catalyst precursor in this reaction, converting to other more active catalytic species in the presence of pFA, resulting in its degradation to CO2 and H2. Nitriles are also showed to play a dual role in this transformation, both as a substrate and as a ligand, where the dimeric catalyst structures convert to monomeric ones upon the coordination of nitrile molecules.
- Tavakoli, Ghazal,Prechtl, Martin H. G.
-
p. 6092 - 6101
(2019/11/11)
-
- Selective Hydrogenation of Carboxylic Acids to Alcohols or Alkanes Employing a Heterogeneous Catalyst
-
The chemoselective hydrogenation of carboxylic acids to either alcohols or alkanes is reported, employing a heterogeneous bimetallic catalyst consisting of rhenium and palladium supported on graphite. α-Chiral carboxylic acids were hydrogenated without loss of optical purity. The catalyst displays a reverse order of reactivity upon hydrogenation of different carboxylic functions with esters being less reactive than amides and carboxylic acids. This allows for chemoselective hydrogenation of an acid in the presence of an ester or an amide function.
- Ullrich, Johannes,Breit, Bernhard
-
p. 785 - 789
(2018/02/14)
-
- Robust cobalt oxide catalysts for controllable hydrogenation of carboxylic acids to alcohols
-
The selective catalytic hydrogenation of carboxylic acids is an important process for alcohol production, while efficient heterogeneous catalyst systems are still being explored. Here, we report the selective hydrogenation of carboxylic acids using earth-abundant cobalt oxides through a reaction-controlled catalysis process. The further reaction of the alcohols is completely hindered by the presence of carboxylic acids in the reaction system. The partial reduction of cobalt oxides by hydrogen at designated temperatures can dramatically enhance the catalytic activity of pristine samples. A wide range of carboxylic acids with a variety of functional groups can be converted to the corresponding alcohols at a yield level applicable to large-scale production. Cobalt monoxide was established as the preferred active phase for the selective hydrogenation of carboxylic acids.
- Song, Song,Wang, Dong,Di, Lu,Wang, Chuanming,Dai, Weili,Wu, Guangjun,Guan, Naijia,Li, Landong
-
p. 250 - 257
(2018/02/20)
-
- Highly Selective Silica-supported Copper Catalysts Derived from Copper Phyllosilicates in the Hydrogenation of Adipic Acid to 1,6-hexanediol
-
Hydrogenation of adipic acid (AA) is a potential way to prepare 1,6-hexanediol (HDOL). Herein, silica-supported copper catalysts derived from copper phyllosilicates were synthesized, characterized, and tested in the hydrogenation of AA to HDOL. In a full conversion of AA, a high yield of HDOL (approximately 90 %) was obtained through the use of each Cu-based catalyst. The turnover frequency calculated according to the consumption rate of AA was discovered to be dependent on the Cu+/(Cu0+Cu+) ratio and the reduction condition. Moreover, recycling tests showed that a catalyst derived from a copper phyllosilicate had better stability compared with Cu/SiO2 made through impregnation due to a stronger interaction between Cu and silica. The kinetic analyses based on the global rate expression and Langmuir?Hinshelwood?Hougen?Watson (LHHW) formalism of AA conversion were conducted. The possible competitive adsorption between AA and its derivatives, including hydroxycaproic acid and ?-caprolactone, was thereby revealed.
- Jiang, Jia-Wei,Tu, Cheng-Chieh,Chen, Chao-Huang,Lin, Yu-Chuan
-
p. 5449 - 5458
(2018/12/04)
-
- Synthesis of 1,6-Hexanediol from Cellulose Derived Tetrahydrofuran-Dimethanol with Pt-WOx/TiO2 Catalysts
-
Cellulose-derived tetrahydrofuran-dimethanol (THFDM) can be converted over Pt-WOx/TiO2 catalysts to 1,6-hexanediol (1,6-HDO) with up to 70% yield. This reaction involves ring-opening of THFDM to 1,2,6-hexanetriol (HTO) and then hydrogenolysis of HTO to 1,6-HDO. Hydrogen atoms spill over from Pt sites onto WOx/TiO2 to reduce the W=O functional group and create Br?nsted acid sites. Similar catalytic activity for THFDM conversion can be been obtained with a physical mixture of Pt/TiO2 and WOx/TiO2 due to hydrogen spillover over spatially separate Pt and WOx when a reducible support (TiO2) is used.
- He, Jiayue,Burt, Samuel P.,Ball, Madelyn,Zhao, Dongting,Hermans, Ive,Dumesic, James A.,Huber, George W.
-
p. 1427 - 1439
(2018/02/14)
-
- Visible-Light-Mediated Aerobic Oxidation of Organoboron Compounds Using in Situ Generated Hydrogen Peroxide
-
A simple and general visible-light-mediated oxidation of organoboron compounds has been developed with rose bengal as the photocatalyst, substoichiometric Et3N as the electron donor, as well as air as the oxidant. This mild and metal-free protocol shows a broad substrate scope and provides a wide range of aliphatic alcohols and phenols in moderate to excellent yields. Notably, the robustness of this method is demonstrated on the stereospecific aerobic oxidation of organoboron compounds.
- Weng, Wei-Zhi,Liang, Hao,Zhang, Bo
-
p. 4979 - 4983
(2018/08/24)
-
- Hydroformylation process for producing 1,6-disubstituted hexane derivatives
-
The invention relates to a process for the production of 1,6-difunctionalized hexane derivatives from 1,3-diunsaturated hydrocarbons, preferably butadiene, wherein a hydroformylation with carbon monoxide and hydrogen is performed in the presence of an at least dihydric alkanol and during the hydroformylation the temperature is increased. The reaction yields the acetals of the 1,6-hexanedial derivatives which are isolated and further reacted to obtain the desired 1,6-difunctionalized hexane derivatives, in particular 1,6-hexanediamine, 1,6-hexanediol and adipic acid.
- -
-
Paragraph 0271; 0272; 0275; 0276
(2018/07/06)
-
- Stabilization of NaBH4 in Methanol Using a Catalytic Amount of NaOMe. Reduction of Esters and Lactones at Room Temperature without Solvent-Induced Loss of Hydride
-
Rapid reaction of NaBH4 with MeOH precludes its use as a solvent for large-scale ester reductions. We have now learned that a catalytic amount of NaOMe (5 mol %) stabilizes NaBH4 solutions in methanol at 25 °C and permits the use of these solutions for the reduction of esters to alcohols. The generality of this reduction method was demonstrated using 22 esters including esters of naturally occurring chiral γ-butyrolactone containing dicarboxylic acids. This method permits the chemoselective reductions of esters in the presence of cyano and nitro groups and the reductive cyclization of a pyrrolidinedione ester to a fused five-membered furo[2,3-b]pyrrole and a (-)-crispine A analogue in high optical and chemical yields. Lactones, aliphatic esters, aromatic esters containing electron-withdrawing groups, and heteroaryl esters are reduced more rapidly than aryl esters containing electron-donating groups. The 11B NMR spectrum of the NaOMe-stabilized NaBH4 solutions showed a minor quartet due to monomethoxyborohydride (NaBH3OMe) that persisted up to 18 h at 25 °C. We postulate that NaBH3OMe is probably the active reducing agent. In support of this hypothesis, the activation barrier for hydride transfer from BH3(OMe)- onto benzoic acid methyl ester was calculated as 18.3 kcal/mol.
- Prasanth,Joseph, Ebbin,Abhijith,Nair,Ibnusaud, Ibrahim,Raskatov, Jevgenij,Singaram, Bakthan
-
p. 1431 - 1440
(2018/02/09)
-
- Remarkably high catalyst efficiency of a disilaruthenacyclic complex for hydrosilane reduction of carbonyl compounds
-
A disilaruthenacyclic complex (1) showed extremely high catalytic activity for hydrosilane reduction of aldehydes and ketones to silyl ethers and secondary and tertiary amides to the corresponding amines. An σ-CAM mechanism was proposed to explain the activity.
- Tahara, Atsushi,Sunada, Yusuke,Takeshita, Takashi,Inoue, Ryoko,Nagashima, Hideo
-
supporting information
p. 11192 - 11195
(2018/10/24)
-
- HYDROFORMYLATION PROCESS FOR PRODUCING 1,6-HEXANEDIOL DERIVATIVES
-
The present invention relates to a two-stage hydroformylation process for producing pound of the formula (I) and to a process for producing a compound of the formula (V) comprising the two-stage hydroformylation process for producing a compound of the formula (I) followed by hydrogenation of the compound of the formula (I).
- -
-
Page/Page column 35; 36
(2019/01/07)
-
- Method for producing 1,6-hexanediol from 1,6-adipic acid by continuous esterification and hydrogenation
-
The invention provides a method for producing 1,6-hexanediol from 1,6-adipic acid by continuous esterification and hydrogenation, belonging to the field of fine chemical synthesis. The method comprises the following steps: carrying out continuous esterification reaction on 1,6-adipic acid and methanol/ethanol in an acid-catalyst-filled reactive distillation tower, carrying out reduced pressure distillation purification on the dimethyl/ethyl adipate, and carrying out hydrogenation to obtain the methanol/ethanol and 1,6-adipic acid, wherein the methanol/ethanol returns to continue esterification, and the 1,6-adipic acid is used as the product. The esterification reaction product yield is 96% or above, and the hydrogenation reaction yield is greater than 99%. The method is simple to operate, implements the continuous esterification-purification-hydrogenation-separation production process, and has favorable economic benefits and industrial application prospects.
- -
-
Paragraph 0026; 0027
(2017/07/20)
-
- POROUS SHAPED METAL-CARBON PRODUCTS
-
The present invention provides a porous metal-containing carbon-based material that is stable at high temperatures under aqueous conditions. The porous metal-containing carbon-based materials are particularly useful in catalytic applications. Also provided, are methods for making and using porous shaped metal-carbon products prepared from these materials.
- -
-
Paragraph 0233-0234
(2017/05/17)
-
- SHAPED POROUS CARBON PRODUCTS
-
Shaped porous carbon products and processes for preparing these products are provided. The shaped porous carbon products can be used, for example, as catalyst supports and adsorbents. Catalyst compositions including these shaped porous carbon products, processes of preparing the catalyst compositions, and various processes of using the shaped porous carbon products and catalyst compositions are also provided.
- -
-
Paragraph 0386-0387
(2017/05/21)
-
- A 5 - hydroxymethyl furfural catalytic conversion of 1, 6 - hexane diol (by machine translation)
-
The present invention provides a 5 - hydroxymethyl furfural catalytic conversion of 1, 6 - hexane diol. The method in order to 5 - hydroxymethyl furfural as raw material, the catalyst active component is M - ReOx load on the catalyst, 50 - 200 °C, hydrogen pressure 1 - 13 mpa after a step under the condition of the catalytic conversion process, the realization of the 5 - hydroxymethyl furfural raw material high-efficiency, high selectivity, high yield in the preparation of 1, 6 - hexanediol. The present invention provides a reaction with raw material from the biomass, the presence of a regeneration, green and the like. At the same time, this reaction the atom economy is high. In addition, with the other in order to biomass as raw materials to make the 1, 6 - hexanediol technical phase comparison, this process has reaction time is short, 1, 6 - hexanediol good selectivity, space-time yield and the like. (by machine translation)
- -
-
Paragraph 0032; 0043; 0046; 0047; 0048; 0049; 0054
(2017/07/22)
-
- Production of 1,6-hexanediol from tetrahydropyran-2-methanol by dehydration-hydration and hydrogenation
-
In this work we present an alternate method for the conversion of tetrahydropyran-2-methanol (THP2M), a cellulose-derived renewable building block, to 1,6-hexanediol (1,6-HDO). Our method is composed of three consecutive steps that either use relatively inexpensive catalysts or no catalyst at all. First, THP2M is catalytically dehydrated to 2,3,4,5-tetrahydrooxepine (THO) in up to 40% yield. THO is then hydrated to 2-oxepanol (OXL) and 6-hydroxyhexanal (6HDHX) with a combined yield of 85% in the absence of a catalyst. OXL and 6HDHX are then quantitatively hydrogenated to 1,6-HDO over a commercially available Ni/C or Ru/C catalyst. Various silicoaluminates were screened for the first acid-catalyzed reaction, and it was found that K-BEA shows the highest THO yield (40% over fresh catalyst, 20% after 25 h on stream). An overall 1,6-HDO yield of 34% from THP2M was obtained.
- Burt, Samuel P.,Barnett, Kevin J.,McClelland, Daniel J.,Wolf, Patrick,Dumesic, James A.,Huber, George W.,Hermans, Ive
-
p. 1390 - 1398
(2017/08/15)
-
- Manganese-Catalyzed Hydrogenation of Esters to Alcohols
-
Homogeneous catalytic hydrogenation of esters to alcohols is an industrially important, environmentally benign reaction. While precious metal-based catalysts for this reaction are now well known, only very few catalysts based on first-row metal complexes were reported. Here we present the hydrogenation of esters catalyzed by a complex of earth-abundant manganese. The reaction proceeds under mild conditions and insight into the mechanism is provided based on an NMR study and the synthesis of novel Mn complexes postulated as intermediates.
- Espinosa-Jalapa, Noel Angel,Nerush, Alexander,Shimon, Linda J. W.,Leitus, Gregory,Avram, Liat,Ben-David, Yehoshoa,Milstein, David
-
supporting information
p. 5934 - 5938
(2017/05/08)
-
- MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
-
The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.
- -
-
Paragraph 00352-00353
(2017/09/05)
-
- Ruthenium-Catalyzed Deaminative Hydrogenation of Aliphatic and Aromatic Nitriles to Primary Alcohols
-
The deaminative hydrogenation of nitriles towards alcohols is a useful reaction to transform nitriles into alcohols with NH3 as the sole byproduct. Using the simple and robust RuHCl(CO)(PPh3)3 complex as a catalyst, at low H2 pressures a series of aliphatic and aromatic nitriles could be transformed into the corresponding alcohols. Suitable solvent systems for these reactions were 1,4-dioxane/water and EtOH/water mixtures. In most cases, the selectivity for the alcohols was excellent, and the corresponding amines were formed only in trace amounts.
- Molnár, István Gábor,Calleja, Pilar,Ernst, Martin,Hashmi, A. Stephen K.,Schaub, Thomas
-
p. 4175 - 4178
(2017/10/09)
-
- Expanding the scope of methyl xanthate esters - From Barton-McCombie reaction auxiliary to versatile protective group
-
The methyl xanthate ester is presented as a versatile protective group for alcohols. Hydroxyl groups can easily be transformed into methyl xanthate esters by several methods and are commonly used as an auxiliary in the Barton-McCombie reaction. We show that these methyl xanthate esters can readily and chemoselectively be cleaved under mild conditions by the action of diethylenetriamine using microwave heating. This method is orthogonal to many common hydroxyl protective groups that can be introduced and cleaved in the presence of methyl xanthate ester.
- Thorsheim, Karin,Manner, Sophie,Ellervik, Ulf
-
p. 6329 - 6333
(2017/09/29)
-
