110028-14-3

Basic information

• Product Name: TRANS CIS-1 9-CYCLOHEXADECADIENE
• Synonyms: TRANS CIS-1 9-CYCLOHEXADECADIENE
• CAS NO: 110028-14-3
• Molecular Formula: C₁₆H₂₈
• Molecular Weight: 220.39352
• Mol File: 110028-14-3.mol

Chemical Properties

• Boiling Point: 315.3±22.0 °C(Predicted)
• Flash Point: 100 °C
• Appearance: /
• Density: 0.814±0.06 g/cm3(Predicted)
• CAS DataBase Reference: TRANS CIS-1 9-CYCLOHEXADECADIENE(CAS DataBase Reference)
• NIST Chemistry Reference: TRANS CIS-1 9-CYCLOHEXADECADIENE(110028-14-3)
• EPA Substance Registry System: TRANS CIS-1 9-CYCLOHEXADECADIENE(110028-14-3)

Safety Data

• Safety Statements: 23-24/25
• Hazardous Substances Data: 110028-14-3(Hazardous Substances Data)

Upstream product

• 931-88-4 1,2-cyclooctene 
• 931-88-4 cis-Cyclooctene 
• 23739-64-2 Hexa-P-phenyl-P,P'-octanediyl-bis-phosphonium bromide 
• 38451-22-8 C₄₄H₄₄P₂ 
• 1720-38-3 1,9-decadiyne 
• 629-03-8 1 ,6-dibromohexane 
• 1697-71-8 cyclohexadeca-1,9-diyne 

Downstream Products

• 3100-36-5 (E/Z)-cyclohexa-dec-8-enone 
• 1235992-15-0 hexadeca-8,15-dienal 
• 956-82-1 3-methylcyclopentadecanone 
• 295-65-8 cyclohexadecane 

Relevant articles and documents

Linker-free, silica-bound olefin-metathesis catalysts: Applications in heterogeneous catalysis

A set of heterogenized olefin-metathesis catalysts, which consisted of Ru complexes with the H2ITap ligand (1,3-bis(2',6'-dimethyl-4'dimethyl aminophenyl)-4,5-dihydroimidazol-2-ylidene) that had been adsorbed onto a silica support, has been prepared. These complexes showed strong binding to the solid support without the need for tethering groups on the complex or functionalized silica. The catalysts were tested in the ring-opening-ring-closing-metathesis (RO-RCM) of cyclooctene (COE) and the self-metathesis of methyl oleate under continuous-flow conditions. The best complexes showed a TON>4000, which surpasses the previously reported materials that were either based on the Grubbs-Hoveyda II complex on silica or on the classical heterogeneous Re 2O7/B2O3 catalyst. Born free: Silica adsorption of ruthenium carbenes with the H2ITap ligand (see figure) yielded heterogeneous materials without the need for tethering groups on the complex or the support. These materials were tested as catalysts in the ring-opening-ring-closing-metathesis of cyclooctene and the cross-metathesis of methyl oleate under continuous-flow conditions. The best complexes showed a TON>4000, which surpasses the most active silica-based materials. Copyright

Bulky N-Phosphino-Functionalized N-Heterocyclic Carbene Ligands: Synthesis, Ruthenium Coordination Chemistry, and Ruthenium Alkylidene Complexes for Olefin Metathesis

Ruthenium chemistry and applications in catalytic olefin metathesis based on N-phosphino-functionalized N-heterocyclic carbene ligands (NHCPs) are presented. Alkyl NHCP Ru coordination chemistry is described, and access to several potential synthetic prec

Dimerisation of cyclooctene using Grubbs' catalysts

The dimerisation of cyclooctene (COE) to 1,9-cyclohexadecadiene, a molecule of interest to the fragrance industry, has been achieved using ruthenium catalysts in organic solvents with significantly better selectivities (47-74%) and yields (39-60%) than previously reported (34% and 30%, respectively). Grubbs' first and second generation catalysts, the Hoveyda-Grubbs' catalyst and a phosphonium alkylidene catalyst were tested in a range of organic solvents and ionic liquids (ILs), including 1:1 IL/dichloromethane mixtures and biphasic IL + pentane systems. The best results (74% selectivity, 60% yield) were obtained using Grubbs' first generation catalyst in 1,2-dichloroethane. The formation of trimer, tetramer and other higher molecular mass products were found to be favoured at low catalyst loadings (0.77 mM). Studies of metathesis reactions using 1,9-cyclohexadecadiene as substrate indicated that the monomer-dimer and monomer-trimer reactions are faster than the dimer-dimer reaction. The use of IL media allowed for the recyclability of the catalyst, although a drop in the yield of dimer generally occurred after the first run. Heterogeneized catalysts, where the IL-catalyst system was immobilised onto silica, resulted in fast reactions leading to poor yields of dimer.

Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow

In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex. In the ring-opening/ring-closing metathesis (RO-RCM; see picture) of cis-cyclooctene, mesoporous silicas (i.e., MCM-41, MCM-48, SBA-15) are preferred supports for homogeneous ruthenium carbenes (see picture). The optimized "linker-free" support showed not only exceptionally high selectivity toward 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry, but is also a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex. Copyright

Methyltrioxorhenium heterogenized on commercially available supporting materials as cyclooctene metathesis catalyst

Methyltrioxorhenium (MTO) is immobilized on various commercially available supporting materials by sublimation under vacuum. Up to 15 wt% MTO (10 wt% Re) can be immobilized on the different supporting materials. Metathesis experiments with cis-cyclooctene as substrate are performed aiming at a high yield of low molecular weight metathesis products (dimers, trimers, tetramers), which are interesting for aroma and flavour industries. Up to ca. 60% of these desired products can be obtained. A high rhenium loading leads usually to good catalytic activities of the materials in the cyclooctene metathesis. Prolonged reaction times lead to higher yields of the high molecular weight metathesis products. When the same catalyst material is used repeatedly in several catalytic runs, leaching of the grafted Re compounds plays an increasing role, resulting in a reduction of the catalyst performance. None of the examined commercially available carrier materials, however, presents an ideal means for the heterogenization of MTO to obtain particularly high amounts of the desired low molecular weight metathesis products of cyclooctene.

Olefin metathesis on a TLC Plate as a Tool for a High-Throughput Screening of Catalyst-Substrate Sets

A methodology for screening either various catalysts for a given metathesis reaction, i.e., ring opening-ring closing alkene metathesis (RO-RCM) and cross-metathesis (CM), or various substrates for a given pre-catalyst on a thin layer chromatography (TLC) plate has been developed. As the substrates elute with the solvent, this TLC-based system acts as a heterogeneous catalyst bed ("TLC reactor"). Selected promising catalyst candidates were screened on a TLC plate and their initial catalytic potential as observed in the TLC test was later fully confirmed in a classical heterogeneous reaction set-up using standard commercially available silica (D11-10). Reacting polyfunctional, natural product-like substrates in our TLC reactor allows the simultaneous screening of various substrates and the convenient micro-scale preparation and isolation of potentially biologically active products. Copyright

Immobilized Grubbs catalysts on mesoporous silica materials: Insight into support characteristics and their impact on catalytic activity and product selectivity

Silica materials show a high ability to physisorb the 2nd generation Hoveyda-Grubbs catalyst (HG2) in organic solvents. The interaction with the complex, likely proceeding through hydrogen bonding, is particularly strong with surfaces rich in silanols, wherein geminal silanols show the highest affinity, and therefore mesoporous silicas are the supports of choice. As long as the silica material is sufficiently pure and free of cages, in which high HG2 concentrations can accumulate, the immobilization of HG2 occurs in a very stable manner. Despite the complex stability, exploration of HG2-loaded mesoporous silica supports in metathesis of cis-cyclooctene indicated significant diffusional and confinement effects, and therefore control of pore size, pore architecture and morphology in balance with the intrinsic catalytic activity is essential for catalyst design. As metathesis of cis-cyclooctene apparently proceeds through the initial formation of linear polymers, followed by backbiting forming cyclic oligomers, potential interference of mass transport and space restriction issues is not surprising. This study shows that the catalyst requirements are best met with the TUD-1 silica support (1.24 wt% HG2). Under such conditions, the heterogeneous catalyst performs as good as the homogeneous one, presenting a thermodynamic distribution of cyclic oligomers. The latter catalyst also showed high catalyst stability in a continuous fixed bed reactor, corresponding to a catalytic turnover number of 18 000. The catalytic rates and catalyst stability are lower when operating in a diffusional regime, therefore long reaction times are required to reach the thermodynamic product distribution. Water removal from the catalyst is also important, not because of HG2 stability reasons, but of lower reaction rates which were measured for hydrated samples, likely due to inhibition of cis-cyclooctene uptake in the pores. Mild removal of physisorbed water before immobilization is therefore advised, for instance by thermal treatments, but care has to be taken to keep the silanol density high for firm HG2 immobilization and also to avoid formation of reactive siloxanes, which chemically react with and destroy HG2. Surprisingly, reactive siloxane formation conditions strongly depend on the silica type, with TUD-1 being fairly sensitive to their formation. Finally, the best HG2-loaded TUD-1 catalyst is used successfully in a broad set of other metathesis reactions.

Evidence for metal-surface interactions and their role in stabilizing Well-defined immobilized Ru-NHC alkene metathesis catalysts

Secondary interactions are demonstrated to direct the stability of well-defined Ru-NHC-based heterogeneous alkene metathesis catalysts. By providing key stabilization of the active sites, higher catalytic performance is achieved. Specifically, they can be described as interactions between the metal center (active site) and the surface functionality of the support, and they have been detected by surface-enhanced 1H-29Si NMR spectroscopy of the ligand and 31P solid-state NMR of the catalyst precursor. They are present only when the metal center is attached to the surface via a flexible linker (a propyl group), which allows the active site to either react with the substrate or relax, reversibly, to the surface, thus providing stability. In contrast, the use of a rigid linker (here mesitylphenyl) leads to a well-defined active site far away from the surface, stabilized only by a phosphine ligand which under reaction conditions leaves probably irreversibly, leading to faster decomposition and deactivation of the catalysts.

USE OF SUPPORTED RUTHENIUM-CARBENE COMPLEXES IN CONTINUOUSLY OPERATED REACTORS

The present invention relates to a process for carrying out a chemical reaction in the presence of a ruthenium-carbene complex supported on silicon dioxide in a continuously operated reactor and also the use of corresponding supported catalysts in continuously operated reactors.

Unsymmetrical Ru-NHC catalysts: A key for the selective tandem Ring Opening-Ring Closing alkene Metathesis (RO-RCM) of cyclooctene

Dissymmetry for selectivity: NHC ligand with two different pendant group allows the selective formation of cyclic oligomers in place of polymers opening new strategy to generate macrocycles. The Royal Society of Chemistry.