2177-81-3

Upstream product

• 592-41-6 1-hexene 
• 110-54-3 hexane 
• 6832-16-2 methyl diazoacetate 
• 67-56-1 methanol 
• 626-93-7 n-hexan-2-ol 
• 201230-82-2 carbon monoxide 
• 623-37-0 n-hexan-3-ol 
• 124-38-9 carbon dioxide 

Downstream Products

• 624-22-6 2-methylhexan-1-ol 
• 1185-29-1 2-methyl-2-ethylhexanoic acid 
• 1065008-64-1 (3aR,4R,5R,6aS)-5-(benzoyloxy)hexahydro-4-[(1E)-4-methyl-3-oxo-1-octenyl]-2H-cyclopenta[b]furan-2-one 
• 1064596-51-5 (3aR,4R,5R,6aS)-5-(benzoyloxy)hexahydro-4-[(1E,3S)-3-hydroxy-4-methyl-1-octenyl]-2H-cyclopenta[b]furan-2-one 
• 1064596-55-9 (3aR,4R,5R,6aS)-5-(benzoyloxy)hexahydro-4-[(1E,3R)-3-hydroxy-4-methyl-1-octenyl]-2H-cyclopenta[b]furan-2-one 
• 1188414-55-2 Toluene-4-sulfonic acid 2-methyl-hexyl ester 
• 17001-24-0 12-methylhexadecanoic acid 
• 101258-57-5 1-bromo-2-methylhexane 
• 95282-68-1 2-Methyl-1,1-bis-(4-methoxy-phenyl)-hexen-⁽¹⁾ 
• 95442-36-7 2-Methyl-1,1-bis-(4-acetoxy-phenyl)-hexen-⁽¹⁾ 
• 1353578-22-9 C₃₃H₂₄F₁₂O 

Relevant academic research and scientific papers

Ruthenium complex immobilized on supported ionic-liquid-phase (SILP) for alkoxycarbonylation of olefins with CO2

In this study, the heterogeneously catalyzed alkoxycarbonylation of olefins with CO2based on a supported ionic-liquid-phase (SILP) strategy is reported for the first time. An [Ru]@SILP catalyst was accessed by immobilization of ruthenium complex on a SILP, wherein imidazolium chloride was chemically integrated at the surface or in the channels of the silica gel support. An active Ru site was generated through reacting Ru3(CO)12with the decorated imidazolium chloride in a proper microenvironment. Different IL films, by varying the functionality of the side chain at the imidazolium cation, were found to strongly affect the porosity, active Ru sites, and CO2adsorption capacity of [Ru]@SILP, thereby considerably influencing its catalytic performance. The optimized [Ru]@SILP-A-2 displayed enhanced catalytic performance and prominent substrate selectivity compared to an independent homogeneous system under identical conditions. These findings provide the basis for a novel design concept for achieving both efficient and stable catalysts in the coupling of CO2with olefins.

Structural studies and applications of water soluble (phenoxy)imine palladium(II) complexes as catalysts in biphasic methoxycarbonylation of 1-hexene

Reactions of the ligands; sodium 4?hydroxy-3-((phenylimino)methyl)benzenesulfonate (L1), sodium 3-(((2,6-dimethylphenyl)imino)methyl)-4-hydroxybenzenesulfonate (L2) and sodium 3-(2,6-diisopropylphenyl)imino)methyl)-4-hydroxybenzenesulfonate (L3) with Pd(OAc)2 afforded the respective palladium(II) complexes [Pd(L1)2] (PdL1), [Pd(L2)2] (PdL2) and [Pd(L3)2] (PdL3). In addition, treatment of the non-water soluble ligands 2-((phenylimino)methyl)phenol (L4), 2-(((2,6-dimethylphenyl)imino)methyl)phenol (L5) and 2-((2,6-diisopropylphenyl)imino)methyl)phenol (L6) with Pd(OAc)2 gave the corresponding complexes [Pd(L4)2] (PdL4), [Pd(L5)2] (PdL5) and [Pd(L6)2] (PdL6) in good yields. Solid state structures of complexes PdL1 and PdL4 established the formation of bis(chelated) square planar neutral compounds. All the complexes formed active catalysts in the methoxycarbonylation of 1-hexene, affording yields of up to 92% within 20 h and regioselectivity of 73% in favour of linear esters. The catalytic activity and selectivity of the complexes depended on the steric encumbrance around the coordination centre. The water soluble complexes displayed comparable catalytic behaviour to the non-water soluble systems. The complexes could be recycled five times with minimal changes in both the catalytic activities and regio-selectivity.

Sterically hindered (pyridyl)benzamidine palladium(II) complexes: Syntheses, structural studies, and applications as catalysts in the methoxycarbonylation of olefins

Reactions of ligands (E)-N′-(2,6-diisopropylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L1), (E)-N′-(2,6-diisopropylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L2), (E)-N′-(2,6-dimethylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L3), (E)-N′-(2,6-dimethylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L4), and (E)-N-(6-methylpyridin-2-yl)-N′-phenylbenzimidamide (L5) with [Pd(NCMe)2Cl2] furnished the corresponding palladium(II) precatalysts (Pd1–Pd5), in good yields. Molecular structures of Pd2 and Pd3 revealed that the ligands coordinate in a N^N bidentate mode to afford square planar compounds. Activation of the palladium(II) complexes with para-tolyl sulfonic acid (PTSA) afforded active catalysts in the methoxycarbonylation of a number of alkene. The resultant catalytic activities were controlled by the both the complex structure and alkene substrate. While aliphatic substrates favored the formation of linear esters (>70%), styrene substrate resulted in the formation of predominantly branched esters of up to 91%.

Palladium(II) complexes of (pyridyl)imine ligands as catalysts for the methoxycarbonylation of olefins

Reactions of 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine (L1), 2-((pyridin-2-yl)methyleneamino)ethanol (L2) and 3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine (L3) ligands with either [PdCl2(COD)] or [PdCl(Me)(COD)] produced the corresponding monometallic complexes [PdCl2(L1)] (1), [PdClMe(L1)] (2), [PdCl2(L2)] (3) and [PdCl2(L3)] (4). The solid state structure of complex 1 confirmed the bidentate coordination mode of L1, giving a distorted square planar geometry. All the complexes (1–4) formed active catalysts for the methoxycarbonylation of higher olefins to give linear and branched esters. The catalytic behavior of complexes 1–4 were influenced by both the complex structure and olefin chain length.

Method for preparing organic carboxylic ester through combined catalysis of aryl bidentate phosphine ligand

The invention discloses a method for preparing organic carboxylic ester by combined catalysis of an aryl bidentate phosphine ligand. The method comprises the following steps: under the action of a palladium compound/aryl bidentate phosphine ligand/acidic additive combined catalyst, carrying out a hydrogen esterification reaction on terminal olefin, carbon monoxide and alcohol so as to generate theorganic carboxylic ester with one more carbon than olefin. According to the invention, by adoption of the palladium compound/aryl bidentate phosphine ligand/acidic additive combined catalyst, good catalytic activity and selectivity for the hydrogen esterification reaction of the olefin are achieved, and olefin carbonylation to synthesize organic carboxylic ester can be efficiently catalyzed. Thearyl bidentate phosphine ligand has a rigid skeleton structure of a rigid ligand and the flexibility of a flexible ligand, so the aryl bidentate phosphine ligand has proper flexibility due to the characteristic that the aryl bidentate phosphine ligand is soft and rigid, and a most favorable coordination mode and a stable active structure in space are favorably formed. In addition, the aryl bidentate phosphine ligand has the advantages of high stability, simple and convenient synthesis method and the like; and a novel industrial technology is provided for production of organic carboxylate compounds.

Methoxycarbonylation of olefins catalysed by homogeneous palladium(II) complexes of (phenoxy)imine ligands bearing alkoxy silane groups

The Schiff base compounds 2-phenyl-2-((3(triethoxysilyl)propyl)imino)ethanol (HL1) and 4-methyl-2-((3(triethoxysilyl)propyl)imino)methyl)phenol (HL2) were synthesized via condensation reactions of a suitable ketone or aldehyde and (3-aminopropyl) triethoxy silane (APTES). Whereas the reactions of HL1 and HL2 with [Pd(OAc)2] afforded the bis(chelated) palladium compounds [Pd(L1)2] (1) and [Pd(L2)2] (2), treatments of HL1 and HL2 with [Pd(NCMe)2Cl2] gave the mono(chelated) complexes [Pd(HL1)2Cl2] (3) and [Pd(HL2)2Cl2] (4) respectively. Structural characterization of the compounds was achieved using NMR and FT-IR spectroscopies, mass spectrometry and micro-analyses. Complexes 1–4 gave active catalysts in the methoxycarbonylation of higher olefins producing linear esters as the major products. The coordination environment around the palladium center of the complexes dictated the relative catalytic activity, where the bis(chelated) analogues 1 and 2 were more active than the mono(chelated) analogues 3 and 4. The nature of the acid promoter, phosphine groups, solvent system, olefin substrate and reactions conditions influenced the catalytic behaviour of the complexes.

Alkoxycarbonylation of olefins with carbon dioxide by a reusable heterobimetallic ruthenium-cobalt catalytic system

The heterobimetallic ruthenium-cobalt catalytic system exhibited good catalytic performance and reusability in the reductive alkoxycarbonylation of olefins with carbon dioxide. Compared to the previous system only consisting of ruthenium catalyst, the binary catalyst system effectively reduced the usage of noble metal and ionic liquid additives. The respective contribution of ruthenium and cobalt catalysts in this multiple-step catalytic process was investigated by a series of condition-controlled experiments. The evolution of the ruthenium catalyst and the occurrence of alkene hydrogenation during the reaction was explained by theortical calculations.

Palladium-Catalyzed Carbonylation of sec- and tert-Alcohols

A general palladium-catalyzed synthesis of linear esters directly from sec- and tert-alcohols is described. Compared to the classic Koch–Haaf reaction, which leads to branched products, this new transformation gives the corresponding linear esters in high yields and selectivity. Key for this protocol is the use of an advanced palladium catalyst system with L2 (pytbpx) as the ligand. A variety of aliphatic and benzylic alcohols can be directly used and the catalyst efficiency for the benchmark reaction is outstanding (turnover number up to 89 000).

Palladium(II) complexes bearing mixed N^N^X (X?=?O and S) tridentate ligands as pre-catalysts for the methoxycarbonylation of selected 1-alkenes

The methoxycarbonylation of selected 1-alkenes catalyzed by various neutral and cationic palladium(II) complexes, containing mixed N^N^X (X = O and S) tridentate ligands 2-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-6-(phenoxymethyl)pyridine (L1), 2-[(3,5-di-tert-butyl-1H-pyrazol-1-yl)methyl]-6-(phenoxymethyl)pyridine (L2), 2-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-6-(phenylthiomethyl)pyridine (L3), 2-[(3,5-di-tert-butyl-1H-pyrazol-1-yl)methyl]-6-(phenylthiomethyl)pyridine (L4), has been investigated. Neutral complexes, [(?2-L1)Pd(CH3)(Cl)] (1a), [(?2-L2)Pd(CH3)(Cl)] (2a), [(?2-L3)Pd(CH3)(Cl)] (3a), [(?2-L4)Pd(CH3)(Cl)] (4a), and the salts, [(?3-L3)Pd(CH3)][BAr4F] (3c) and [(?3-L4)Pd(CH3)][BAr4F] (4c), underwent complete decomposition during the reaction to palladium black and showed no catalytic activity. However, the addition of PPh3 to the reaction dramatically increased the catalytic activity. On the other hand, the salts, [(?2-L1)Pd(CH3)(PPh3)][BAr4F] (1b), [(?2-L2)Pd(CH3)(PPh3)][BAr4F] (2b), [(?2-L3)Pd(CH3)(PPh3)][BAr4F] (3b) and [(?2-L4)Pd(CH3)(PPh3)][BAr4F] (4b), showed good conversion of the selected olefins to branched and linear esters without PPh3. Addition of PPh3 to reactions with 1b-4b significantly improved catalytic activity. All decomposition of complexes led to the formation of the known palladium complexes, [Pd(PPh3)2(Cl)(CH3)] and [Pd(PPh3)2Cl2]. The decomposition of all palladium complexes could be followed by NMR studies and [Pd(PPh3)2Cl2] could be isolated from the crude methoxycarbonylation reaction.

Toward the development of efficient and stable Pd-catalysts for the methoxycarbonylation of medium chain alkenes

Methoxycarbonylation provides a one-step synthesis to valuable ester products utilised in both the fine and heavy chemical industry. However, in general, reaction rates for longer chain alkenes are poor which renders industrial implementation economical unviable. In cases where suitable rates are achieved, the requisite reagents are costly and in addition, the catalyst complexes readily decompose at elevated temperatures. This paper describes the use of an alternative ligand structural motif for the efficient methoxycarbonylation of terminal and internal medium chain alkenes to their corresponding esters. Promising results were obtained using a catalyst complex generated in situ from an unsymmetrical diphosphine ligand based on a ferrocene backbone, Pd(OAc)2 and methane sulfonic acid.