629-30-1Relevant articles and documents
Hydroformylation reaction ligand, hydroformylation catalyst and diol preparation method
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Paragraph 0079-0080, (2021/06/22)
The invention discloses a hydroformylation reaction ligand, a hydroformylation catalyst and a diol preparation method According to the invention, the structural formula of the hydroformylation reaction ligand is shown in the specification, wherein R1 and R2 are mutually independent one of H, aryl or substituted aryl, thienyl, pyrrolyl, thiazolyl, imidazolyl and pyridyl; the ligand disclosed by the invention is high in catalytic activity and good in metal active center stability, by-products of aldehyde in a conventional hydroformylation reaction can be reduced, and linear diol with a high normal/isomer ratio can be obtained by a one-step method; and 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.
Experimental and Computational Studies of Palladium-Catalyzed Spirocyclization via a Narasaka-Heck/C(sp3or sp2)-H Activation Cascade Reaction
Wei, Wan-Xu,Li, Yuke,Wen, Ya-Ting,Li, Ming,Li, Xue-Song,Wang, Cui-Tian,Liu, Hong-Chao,Xia, Yu,Zhang, Bo-Sheng,Jiao, Rui-Qiang,Liang, Yong-Min
supporting information, p. 7868 - 7875 (2021/05/27)
The first synthesis of highly strained spirocyclobutane-pyrrolines via a palladium-catalyzed tandem Narasaka-Heck/C(sp3 or sp2)-H activation reaction is reported here. The key step in this transformation is the activation of a δ-C-H bond via an in situ generated σ-alkyl-Pd(II) species to form a five-membered spiro-palladacycle intermediate. The concerted metalation-deprotonation (CMD) process, rate-determining step, and energy barrier of the entire reaction were explored by density functional theory (DFT) calculations. Moreover, a series of control experiments was conducted to probe the rate-determining step and reversibility of the C(sp3)-H activation step.
Short and Easily Scalable Synthesis of the Sex Pheromone of the Horse-Chestnut Leaf Miner (Cameraria ohridella) Relying on a Key Ligand- And Additive-Free Iron-Catalyzed Cross-Coupling
Chourreu, Pablo,Gayon, Eric,Guerret, Olivier,Guillonneau, Lo?c,Lefèvre, Guillaume
, p. 1335 - 1340 (2020/08/14)
We describe in this work a short six-step convergent high-scale synthesis of the sex pheromone of the horse-chestnut leaf miner ((8E,10Z)-tetradeca-8,10-dienal). This procedure relies on a key stereoselective iron-catalyzed Kumada cross-coupling, which affords the coupling product in high yield in the absence of additional ligands or additives. DFT calculations moreover suggest that ω-alkoxide groups on iron-ligated chains in transient organoiron(II) intermediates can enhance their stability and hamper their decomposition in off-cycle β-hydride elimination reactions.
One-pot biosynthesis of 1,6-hexanediol from cyclohexane by: De novo designed cascade biocatalysis
Kang, Lixin,Li, Aitao,Li, Qian,Li, Renjie,Wang, Fei,Yu, Xiaojuan,Zhang, Zhongwei,Zhao, Jing
, p. 7476 - 7483 (2020/11/23)
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
A acetic acid 7 E, 9 Z - twelve carbon two alkene ester synthesis method (by machine translation)
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Paragraph 0117-0121; 0135-0139, (2019/05/08)
The present invention provides a kind of acetic acid 7 E, 9 Z - twelve carbon two alkene ester synthesis method, which belongs to the technical field of organic synthesis. The present invention provides a method to synthesis of 1, 5 - dibromo-pentane as the starting material for the preparation of 1, 7 - heptyl glycol, then single-esterification reaction to produce acetic acid 7 - hydroxy heptyl esters, acetic acid 7 - hydroxy heptyl esters obtained after the oxidation of acetic acid 7 - [...], acetic acid 7 - [...] 1st Wittig reagent occurs with the 1st Wittig reaction, by hydrolytic reaction, to obtain acetic acid 9 - oxo - 7 E - [...], acetic acid 9 - oxo - 7 E - [...] 2nd Wittig reagent occurs with the 2nd Wittig reaction, to obtain acetic acid 7 E, 9 Z - [...], the route the required raw materials are cheap and easy to get, only five-step to get the final product. (by machine translation)
A smarter approach to catalysts by design: Combining surface organometallic chemistry on oxide and metal gives selective catalysts for dehydrogenation of 2,3-dimethylbutane
Rouge, Pascal,Garron, Anthony,Norsic, Sébastien,Larabi, Cherif,Merle, Nicolas,Delevoye, Laurent,Gauvin, Regis M.,Szeto, Kai C.,Taoufik, Mostafa
, p. 21 - 26 (2019/04/25)
2,3-dimethylbutane is selectively converted into 2,3-dimethylbutenes at 500 °C under hydrogen or at 390 °C under nitrogen in the presence of bimetallic catalysts Pt-Sn/Li-Al2O3. The high stability of the catalyst along the reaction is obtained by selective modification of the Pt/Li-Al2O3 catalyst using Surface Organometallic Chemistry (SOMC).
Method for preparing 2,3-dimethyl-1-butene by dimerization of propylene
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Paragraph 0026-0065, (2019/07/29)
The invention provides a method for preparing 2,3-dimethyl-1-butene by dimerization of propylene. According to the method, a catalytic system comprises a catalyst, a cocatalyst and a ligand, wherein the ligand is organic phosphorus. The method disclosed by the invention has relatively high selectivity and catalytic activity on 2,3-dimethyl-1-butene. The catalytic system can keep lower reaction temperature and lower reaction pressure (compared with the temperature and pressure of an isomerization process in the prior art), the conditions are mild, the safety coefficient is relatively high, production requirements can be met by general chemical production equipment, and the method is suitable for amplifying production. The catalyst is simple to prepare and is low in cost and good in stability. The catalyst is easier to separate from a reaction system by adopting a metal nickel simple substance for loading, and catalytic active components are not lost easily.
Room Temperature Iron-Catalyzed Transfer Hydrogenation and Regioselective Deuteration of Carbon-Carbon Double Bonds
Espinal-Viguri, Maialen,Neale, Samuel E.,Coles, Nathan T.,MacGregor, Stuart A.,Webster, Ruth L.
supporting information, p. 572 - 582 (2019/01/08)
An iron catalyst has been developed for the transfer hydrogenation of carbon-carbon multiple bonds. Using a well-defined β-diketiminate iron(II) precatalyst, a sacrificial amine and a borane, even simple, unactivated alkenes such as 1-hexene undergo hydrogenation within 1 h at room temperature. Tuning the reagent stoichiometry allows for semi- and complete hydrogenation of terminal alkynes. It is also possible to hydrogenate aminoalkenes and aminoalkynes without poisoning the catalyst through competitive amine ligation. Furthermore, by exploiting the separate protic and hydridic nature of the reagents, it is possible to regioselectively prepare monoisotopically labeled products. DFT calculations define a mechanism for the transfer hydrogenation of propene with nBuNH2 and HBpin that involves the initial formation of an iron(II)-hydride active species, 1,2-insertion of propene, and rate-limiting protonolysis of the resultant alkyl by the amine N-H bond. This mechanism is fully consistent with the selective deuteration studies, although the calculations also highlight alkene hydroboration and amine-borane dehydrocoupling as competitive processes. This was resolved by reassessing the nature of the active transfer hydrogenation agent: experimentally, a gel is observed in catalysis, and calculations suggest this can be formulated as an oligomeric species comprising H-bonded amine-borane adducts. Gel formation serves to reduce the effective concentrations of free HBpin and nBuNH2 and so disfavors both hydroboration and dehydrocoupling while allowing alkene migratory insertion (and hence transfer hydrogenation) to dominate.
Synthetic method of 7-bromine-1-heptanol
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Paragraph 0012; 0013; 0014, (2018/04/01)
The invention provides a synthetic method of 7-bromine-1-heptanol. The synthetic method includes synthesizing dimethyl pimelate, 1, 7-heptandiol and 7-bromine-1-heptanol sequentially. The synthetic method has the advantages that the synthetic method is simple to operate and low in cost; through strict control of consumption and reaction time of hydrobromic acid, reaction conversion rate is increased, generation of dibromo-products is reduced greatly, and product purity, yield and productivity are improved; the content reaches more than 99%, and industrial production is facilitated.
MANUFACTURING METHOD OF LINEAR OR BRANCHED DIOL
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Paragraph 0023; 0031, (2018/04/10)
PROBLEM TO BE SOLVED: To manufacture diol having 6 or more carbon atoms at a low cost. SOLUTION: There is provided a manufacturing method of long chain linear or branched diol, by a hydrogenation reaction of a compound having a carbon chain with 1 to 4 carbon atoms between a furan ring and an aldehyde group in presence of a solid catalyst to manufacture diol having 6 to 9 carbon atoms. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
