1117-90-4

Upstream product

• 187737-37-7 propene 
• 1517-52-8 hexadeuteriopropene 
• 7299-37-8 methylacetylene-d1 
• 1184-59-4 propene-2-d1 
• 590-14-7 1-bromo-1-propene 
• 3728-37-8 (Z)-vinyl chloride-d1 
• 4984-12-7 d1-vinyl chloride 
• 181707-48-2 [((2,6-iPr₂C₆H₃)NC(Me)C(Me)N(2,6-iPr₂C₆H₃))Pd(Et₂O)Me]SbF₆ 
• 7647-01-0 hydrogenchloride 
• 110221-72-2 C₆H₁₀⁽²⁾H₂ 
• 97935-37-0 (1R,2S,3S- and 1S,2R,3R)-3-deuterio-2-methyl-1-aminocyclopropane-1-carboxylic acid 
• 97935-37-0 (1R,2S,3R- and 1S,2R,3S)-3-deuterio-2-methyl-1-aminocyclopropane-1-carboxylic acid 
• 97935-37-0 C₅H₈⁽²⁾HNO₂ 
• 97935-37-0 C₅H₈⁽²⁾HNO₂ 

Downstream Products

• 2813-62-9 (Z)-1,2-Dideuterioethylen 
• 590-18-1 (Z)-2-Butene 
• 624-64-6 trans-2-Butene 
• 1517-53-9 (E)-ethene-1,2-d2 
• 1117-91-5 trans-propene-d1 
• 43351-10-6 (E)-propene-1-d5 

Relevant academic research and scientific papers

Zr-alkyl isomerization in ansa-zirconocene-catalyzed olefin polymerizations. Contributions to stereoerror formation and chain termination

In polymers made from (E)- or (Z)-[1-D]propene with methyl alumoxane (MAO)-activated ansa-zirconocene catalysts, signals of deuterium-labeled mrrm pentads document that stereoerrors arise mainly from an isomerization of the Zr-bound chain end. Reduced D-atom redistribution in poly( [2-D]propene) indicates a kinetic isotope effect of k(H)/k(D) ~ 3 for the β-H/D transfer associated with the isomerization reaction. In all poly([1- and [2-D]propenes) studied, D-labeled mmmm pentads occur with a probability similar to that of D-labeled mrrm pentads; this observation requires further mechanistic clarification. Olefinic chain ends of polymers obtained with C2H4(thind)2ZrCl2-MAO from (E)- or (Z)-[1-D]propene deviate in their D-label distributions from the expected stereochemistry. Isomerization of the Zr-bound chain end, probably via a Zr-bound tertiary alkyl intermediate, thus contributes also to chain-growth termination. With the sterically hindered catalyst Me2Si(2-Me-4-tBu-C5H2)2ZrCl2-MAO, almost all chain terminations appear to occur via chain-end isomerization, which does not lead to stereoerrors here. With the high-performance catalyst Me2Si(2-Me-benz[e]indenyl)2ZrCl2-MAO, finally, no D-label is found in the mrrm and mmmm pentad signals; here, Zr-alkyl isomerization can apparently not compete with the high rate of olefin insertion.

Mechanism of the reaction of vinyl chloride with (α-diimine)PdMe + species

The reaction of vinyl chloride (VC) with (α-diimine)PdMe+ species yields (α-diimine)PdCl(propene)+. Isotope labeling experiments using the deuterium-labeled vinyl chlorides 1-VC-d1 and Z-VC-d1 combined with DFT

Oxygen-containing, asymmetric "dual-side" zirconocenes: Investigations on a reversible chain transfer to aluminum

A series of new oxygen-substituted, asymmetric zirconocene dichlorides (rac-{1-[5,6-(ethylenedioxy)-2-methyl-1-η5-indenyl]-2- (9-η5-fluorenyl)ethane}zirconium dichloride (3a), rac{1-[5,6-(ethylenedioxy)-2-methyl-1-η5-indenyl]-2- (9-η5-fluorenyl)ethane}dimethylzirconium (3b) and rac-{[5,6-ethylenedioxy)-2-methyl-1-η5-indenyl] (9-η5-fluorenyl) dimethylsilane} zirconium dichloride (3c)} have been prepared and their polymerization behavior was investigated in dependence of monomer concentration, temperature and catalyst activation. The presence of oxygen substituents on the indenyl ring results in a strong increase of polymerization activities and also of polymer molecular weights with decreasing Al/Zr ratio. Significantly higher molecular masses and activities were found for the dimethyl complex 3b after activation with [(C6H5)3C+] [(C6F5)4B-] deriving from the absence of chain transfer to aluminum and higher concentration of active cata lyst species. The mechanism of stereoerror formation of the oxygen-containing C1-symmetric catalyst was investigated by deuterium labeling studies on propene monomers. The results are discussed on the basis of a reversible chain transfer to aluminum.

Novel Support Effects on the Mechanism of Propene-Deuterium Addition and Exchange Reactions over Dispersed ZrO2

The effect on the rate and mechanisms of propene-deuterium reactions of dispersing ZrO2 on various supports such as silica, alumina, and titanium dioxide has been studied by microwave spectroscopic analysis of monodeuteropropene as well as by kinetic investigation.By dispersal of ZrO2 on these supports, the rate of the C3H6-D2 reactions is increased considerably compared to that over unsupported ZrO2, with the decrease of activation energy.Hydrogen exchange in propene proceeds simultaneously with addition via the associative mechanism through n-propyl and s-propyl intermediates.Through XPS analysis of ZrO2/SiO2, it was found that a monolayer of ZrO2 is formed over the silica support.The monolayer catalyst exhibits catalytic behavior quite different from that of unsupported ZrO2.On the other hand, alumina surfaces modified by ZrO2 layers may be the main active sites in the case of ZrO2/Al2O3.The marked enhancement of the reaction rate in the lower loading region of ZrO2/TiO2 may be explained by the strong interaction of atomically dispersed zirconium ions with active centers on TiO2

Mechanism of Propene-Deuterium Addition and Exchange Reaction over Silica-Supported ZrO2

The mechanism of propene-deuterium reaction over unsupported and silica-supported ZrO2 catalysts was studied with kinetic investigation as well as microwave spectroscopic analysis of monodeuteriopropene. Unsupported ZrO2 exhibited the identical catalytic behavior for C3H6-D2 reaction with other oxide catalysts previously reported: Only propane-d2 was selectively formed in the addition process, with no hydrogen exchange in propene. By supporting on silica, the rate of C3H6-D2 reaction increased considerably, with the decrease of activation energy. Hydrogen exchange in propene proceeded simultaneously with addition via associative mechanism through propyl and isopropyl intermediates. Small particles of ZrO2 were proposed as active sites of this characteristic catalytic behavior.

Marked Size Effect of Zinc Oxide Particles Supported on Silica in Propene-Deuterium Addition and Exchange Reactions

Small particles of ZnO trapped between silica particles exhibit a marked size effect on the reaction rates as well as on the reaction intermediates of the propene-deuterium addition and exchange reactions.

Remarkable Dispersion Effect of TiO2 Catalyst on Silica Support in Propene - Deuterium Addition and Exchange Reaction

Investigation on the effect of dispersing small particles of TiO2 over silica upon the rate and mechanism of propene-deuterium reaction revealed that lower loading catalysts (1-8 wtpercent) exhibit markedly different catalytic behavior from that over unloaded TiO2.

Synergetic Ligand Effect in the Hydrogen Exchange Reaction of Propene over Pd-Cu and Pt-Cu Alloy Catalysts

Marked changes of reation intermediates on alloying were disclosed by the microwave spectroscopic analysis of the monodeuteriopropene formed during C3H6-C3D6 exchange reaction over Pd-Cu and Pt-Cu alloy catalysts.

Mechanism of Deuterium Addition and Exchange of Propene over Silica-supported Gold and Silver Catalysts

The mechanism of the C3H6-D2 reaction over silica-supported Au and Ag catalysts has been studied by applying microwave spectroscopy as well as kinetic measurements.A large kinetic isotope effect was observed for the rate of propane formation between the C3H6-H2 andC3H6D2 reactions, indicating that the hydrogen dissociation is the rate-determining step.Both deuterium addition and exchange processes proceeded via an associative mechanism involving n-propyl as well as s-propyl species, although the methyl hydrogen of propene was less active for exchange through this process.In addition, intramolecular 1,3- and 2,3-hydrogen-shift processes were observed for the first time; they proceeded only in the presence of gaseous hydrogen and caused the exchange of the methyl hydrogen of propene.The characteristic features of supported Group IB metals in this reaction are compared with those of Group VIII metals, and the possible structures of reaction intermediates are discussed in detail.

A Stereochemical Study of the Thermolysis of cis-anti- and trans-1,2-Dimethyl-cis-3,4-dideuteriocyclobutane

The stereochemistry of the fragmentation and isomerization of cis-anti- and trans-1,2-dimethyl-cis-3,4-dideuteriocyclobutane at 510 deg C is reported.The cis-anti-cis isomer undergoes fragmentation to yield cis/trans-propene-d1 (1.5/1, major pathway), cis/trans-2-butene (1.4/1), and cis/trans-ethylene-d2 (1/1, minor pathway).Recovered cis-1,2-dimethylcyclobutane-d2 containing approximately 40percent of the double rotation product relative to the product of single methyl rotation, trans-1,2-dimethylcyclobutane-d2.The trans isomer behaves similarly, yielding cis/trans-propene-d1 (1/1, major pathway), cis/trans-2-butene (1/5), and cis/trans-ethylene-d2 (1/1, minor pathway).Recovered cis-1,2-dimethylcyclobutane-d2 from thermolysis of the trans isomer consists mainly of equal amounts of cis-anti-cis- and cis-syn-cis-1m2-dimethylcyclobutane-d2 as analyzed by NMR.On the basis of product composition, the thermal chemistry of this system can be explained as proceeding through 2,5-hexanediyl (major pathway) and 3-methyl-1,4-pentanediyl (minor pathway).On the basis of the observed stereochemistry, it can be concluded that the lifetimes of both 2,5-hexanediyl and 3-methyl-1,4-pentanediyl are similar and of the same order as bond rotations at a radical center.This suggests that the gauche to trans conformational changes involving carbon-carbon bond rotation at carbon 2 and 3 of 1,4-diyls may not be competitive with fragmentation.