123-01-3Relevant articles and documents
Roles of supports on reducibility and activities of Cu3P catalysts for deoxygenation of oleic acid: In situ XRD and XAS studies
Kochaputi, Nopparuj,Khemthong, Pongtanawat,Kasamechonchung, Panita,Butburee, Teera,Limphirat, Wanwisa,Poo-arporn, Yingyot,Kuboon, Sanchai,Faungnawakij, Kajornsak,Kongmark, Chanapa
, (2022)
This work demonstrates for the first time that SiO2 and ultra-stable zeolite Y (USY) supports play significant roles in the reducibility of Cu2P2O7 to form Cu3P, which consequently affects the selectivity of oleic acid deoxygenation. The formation of supported Cu3P nanoparticles during hydrogen reduction of Cu2P2O7 was carefully investigated by in situ X-ray diffraction (in situ XRD), and in situ X-ray absorption spectroscopy (in situ XAS). The results indicate that the transformation of Cu2P2O7 to Cu3P occurs through several steps. In the first step, all supported Cu2P2O7 precursors are reduced to metallic Cu. Then, copper particles on SiO2 support react with phosphorus compounds and directly transform to Cu3P. On the other hand, copper particles on USY support partially transform to CuP2 and Cu(OH)2 before all converting to Cu3P. Despite multi-step transformations, Cu2P2O7/USY exhibits the lowest onset reduction temperature and provides Cu3P with a small particle size. The deoxygenation of oleic acid over Cu3P supported catalysts reaches nearly 100 % conversion. Both catalysts favor cyclization and aromatization to form cyclic and aromatic compounds. Cu3P/SiO2 achieves higher dodecylbenzene yield (46 %) than Cu3P/USY (33 %). A proposed mechanism consists of hydrogenation of oleic acid and deoxygenation, then followed by cracking, cyclization, aromatization, and alkyl rearrangement.
Durability enhanced ionic liquid catalyst for Friedel-Crafts reaction between benzene and 1-dodecene: Insight into catalyst deactivation
He, Yibo,Wan, Chao,Zhang, Qinghua,Zhan, Xiaoli,Cheng, Dang-Guo,Chen, Fengqiu
, p. 62241 - 62247 (2015)
Friedel-Crafts alkylation of benzene with 1-dodecene, which is an important reaction of synthetic detergent, was studied using the catalyst [bmim][TFSI]/AlCl3 (1-butyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide/AlCl3). These ionic liquid catalysts show biphasic behaviors at a specific condition. Active site species and Lewis acidity were determined by NMR and acetonitrile probe FT-IR. NMR spectroscopy investigations indicated that coordinated and uncoordinated [TFSI]- existed in the ionic liquid catalyst system simultaneously, while tetrahedral 4-coordinate Al2Cl7- was the main active species for Friedel-Crafts alkylation. The complex [AlClx(TFSI)y]- tends to decompose and release 4-coordinated Al2Cl7- and [TFSI]-. The phase behavior study of the ionic liquid [bmim][TFSI]/AlCl3 demonstrated that the upper phase could be used as an efficient heterogeneous catalyst when AlCl3/IL ≥ 1.5. Due to the presence of the anion [TFSI]- around the active sites, especially [TFSI]- at the uncoordinated state, the ionic liquid formed a stable and hydrophobic chemical environment, which enhanced catalyst durability. The influence of various reaction conditions including catalyst reusability on the alkylation reaction was studied, and the potential reasons for catalyst deactivation were discussed. The highest 2-LAB selectivity was more than 50% when 1-dodecene conversion was nearly 100%. Compared with liquid or solid acid catalyst, ionic liquid catalysts have many advantages concerning energy and the environment.
Borane evolution and its application to organic synthesis using the phase-vanishing method
Soga, Nene,Yoshiki, Tomo,Sato, Aoi,Kawamoto, Takuji,Ryu, Ilhyong,Matsubara, Hiroshi
, (2021/03/26)
Although borane is a useful reagent, it is difficult to handle. In this study, borane was generated in situ from NaBH4 or nBu4NBH4 with several oxidants using a phase-vanishing (PV) method. The borane generated was directly reacted with alkenes, affording the desired alcohols in good yields after oxidation with H2O2 under basic conditions. The selective reduction of carboxylic acids with the evolved borane was examined. The organoboranes generated by the PV method successfully underwent Suzuki–Miyaura coupling. Using this PV system, reactions with borane can be carried out easily and safely in a common test tube.
Dumbbell-Shaped 2,2’-Bipyridines: Controlled Metal Monochelation and Application to Ni-Catalyzed Cross-Couplings
Kim, Yongjoon,Iwai, Tomohiro,Fujii, Sho,Ueno, Kosei,Sawamura, Masaya
supporting information, p. 2289 - 2293 (2020/12/07)
2,2’-Bipyridine ligands (dsbpys) with dumbbell-like shapes and differently substituted triarylmethyl groups at the C5 and C5’ positions showed high ligand performance in the Ni-catalyzed cross-electrophile coupling and the Ni/photoredox-synergistically catalyzed decarboxylative coupling reactions. The superior ligand effects of dsbpys compared to the conventional bpy ligands were attributed to the monochelating nature of dsbpys.
Iron-catalysed allylation-hydrogenation sequences as masked alkyl-alkyl cross-couplings
Bernauer, Josef,Wu, Guojiao,Von Wangelin, Axel
, p. 31217 - 31223 (2019/10/19)
An iron-catalysed allylation of organomagnesium reagents (alkyl, aryl) with simple allyl acetates proceeds under mild conditions (Fe(OAc)2 or Fe(acac)2, Et2O, r.t.) to furnish various alkene and styrene derivatives. Mechanistic studies indicate the operation of a homotopic catalyst. The sequential combination of such iron-catalysed allylation with an iron-catalysed hydrogenation results in overall C(sp3)-C(sp3)-bond formation that constitutes an attractive alternative to challenging direct cross-coupling protocols with alkyl halides.
A process for preparing long-chain alkyl benzene (by machine translation)
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Paragraph 0080-0088; 0098-0101, (2019/05/16)
The invention discloses a process for preparing long-chain alkyl benzene, including: the [...] chain alkyl agent in the metal compound assistants and the presence of the ionic liquid catalyst for carrying out the alkylation reaction, containing the reaction product of the long-chain alkyl benzene; wherein the alkylating agent is C states the long chain10 - C18 Straight-chain olefin or halide; said ionic liquid catalyst comprises a cation and anion, the cation is selected from the isoquinoline kind of positive ion, quinoline kind of positive ion and benzimidazole in at least one of the kind of positive ion, the anion is selected from sulfuric acid hydrogen radical, trifluoromethanesulfonic acid radical, the dihydrogen phosphates, paratoluene sulfonic acid, trifluoroacetic acid radical, four fluorophosphoric acid radical and six fluoboric acid in the root of the at least one. The method of the invention the kind of positive ion cation is isoquinoline, quinoline kind of positive ion or benzimidazole kind of positive ion of the ionic liquid as catalyst, to mix with the additive for preparing long-chain alkylbenzene, mild reaction conditions, the reaction conversion rate of raw materials is high, the product has good choice. (by machine translation)
METHOD OF REPROCESSING ALKANESULFONIC ACID
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Paragraph 0129, (2018/12/04)
The invention relates to a method of reprocessing alkanesulfonic acid employed in a chemical process as an agent, catalyst or solvent and comprising the steps of: (a) removing an alkanesulfonic acid-comprising stream from a reaction mixture generated in the chemical process,(b) feeding the alkanesulfonic acid-comprising stream into a melt crystallization as the starting melt to form crystals of the alkanesulfonic acid, of hydrates of the alkanesulfonic acid or of a mixture of both suspended in mother liquor,(c) performing a solid-liquid separation to remove the crystals from the mother liquor,(d) optionally washing the crystals to remove mother liquor adhering to the crystals,(e) recycling the washed or unwashed crystals removed from the mother liquor into the chemical process.
Metathesis of renewable polyene feedstocks – Indirect evidences of the formation of catalytically active ruthenium allylidene species
Kovács, Ervin,Sághy, Péter,Turczel, Gábor,Tóth, Imre,Lendvay, Gy?rgy,Domján, Attila,Anastas, Paul T.,Tuba, Róbert
supporting information, p. 213 - 217 (2017/09/12)
Cross-metathesis (CM) of conjugated polyenes, such as 1,6-diphenyl-1,3,5-hexatriene (1) and α-eleostearic acid methyl ester (2) with several olefins, including 1-hexene, dimethyl maleate and cis-stilbene as model compounds has been carried out using (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)-dichloro(o-isopropoxyphenylmethylene)ruthenium (Hoveyda-Grubbs 2nd generation, HG2) catalyst. The feasibility of these reactions is demonstrated by the observed high conversions and reasonable yields. Thus, regardless of the relatively low electron density, =CH–CH= conjugated units of molecules, including compound 2 as a sustainable, non-foodstuff source, can be utilized as building blocks for the synthesis of various value-added chemicals via olefin metathesis. DFT-studies and the product spectrum of the self-metathesis of 1,6-diphenyl-1,3,5-hexatriene suggest that a Ru η1-allylidene complex is the active species in the reaction.
Alkyl diphenyl phosphine and preparing alkyl diphenyl phosphine payment proportional to production alkyl benzene
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Paragraph 0074; 0078-0081, (2017/08/25)
The invention discloses alkyl diphenylphosphine and a method for preparing alkyl diphenylphosphine with co-production of alkylbenzene. The structural formula of alkyl diphenylphosphine is shown in a formula I. The method comprises: adding triphenylphosphine and metal lithium into an organic solvent for reaction for 3-6 hours at room temperature; and cooling the reaction system to 0-10 DEG C, adding halogenated straight-chain alkane for insulating reaction, then raising the temperature of the system to 30-80 DEG C, keeping the temperature to react for 1-3 hours, removing the organic solvent and reducing the pressure and distilling to separately obtain alkyl diphenylphosphine and alkylbenzene. According to the alkyl diphenylphosphine disclosed by the invention, alkyl is directly bonded with P, so that the alkyl diphenylphosphine can be dissolved in most solvents and can be used as a ligand for homogeneous catalysts. By virtue of the method disclosed by the invention, high value straight-chain alkylbenzene is co-produced while straight-chain alkyl diphenylphosphine is prepared by way of a one-pot process. Use of chloro-tert-butane which is relatively high in price and waste of the metal lithium are avoided. The method is simple to operate, efficient, low in energy consumption, low in cost and suitable for large-scaled industrial production.
Copper-catalyzed cross-coupling reactions of non-activated primary, secondary or tertiary alkyl chlorides with phenylmagnesium bromide
Tao, Chuanzhou,Sun, Lei,Wang, Bin,Liu, Zhou,Zhai, Yadong,Zhang, Xiulian,Shi, Dahua,Liu, Weiwei
supporting information, p. 305 - 308 (2017/01/03)
Efficient copper-catalyzed cross-coupling reactions of non-activated alkyl chlorides, including primary, secondary, and tertiary alkyl chlorides, with phenyl Grignard reagents were achieved. Preparation of phenylmagnesium bromide in 2-methyltetrahydrofuran is critical for the success of the reaction. This protocol expands the synthetic toolbox for the construction of C[sbnd]C bonds of non-activated primary, secondary, and tertiary alkyl chlorides via copper-catalyzed cross-coupling.
