5116-65-4

Upstream product

• 632-21-3 1,1,3,3-tetrachloropropanone 
• 100-40-3 4-ethenylcyclohexene 
• 1774-47-6 trimethylsulfoxonium iodide 
• 100-50-5 3-Cyclohexene-1-carboxaldehyde 
• 1059150-27-4 trimethylsulfonium methyl sulfate 
• 67-56-1 methanol 

Downstream Products

• 64011-53-6 4-(1,2-dihydroxyethyl)cyclohexene 

Relevant academic research and scientific papers

Syntheses and spectroscopic characterizations of oxidative metabolites of 4-vinylcyclohexene

The 7,8-epoxide and 7,8-diol derivatives of 4-vinylcyclohexene were prepared and characterized spectroscopically for use as standards in toxicological studies of the oxidative metabolism of the parent hydrocarbon.

Stereochemical aspects in the 4-vinylcyclohexene biotransformation with rat liver microsomes and purified P450s. Monoepoxides and diols

The stereochemical course of the biotransformation of 4-vinylcyclohexene (VCH, 1) by liver microsomes from male and female control and induced rats and purified rat P450 2B1 and 2E1 has been determined. The epoxidation of 1, catalyzed by male microsomes, occurs on both the endo- and exocyclic double bond to give four isomeric epoxides, cis-4-vinylcyclohexene 1,2-epoxide (2), trans-4-vinylcyclohexene 1,2-epoxide (3), (4R*,7S*)-4-vinylcyclohexene 7,8-epoxide (4), and (4R*,7R*)-4-vinylcyclohexene 7,8-epoxide (5). On the other hand, microsomes from female rats catalyzed primarily the endocyclic epoxidation. The stereoselectivity of this process was strongly dependent on gender and P450 induction. Only the phenobarbital and pyrazole, at lower levels, were able to enhance the epoxidation of 1 and mostly on the endocyclic double bond. Also, P450 2E1 and 2B1 in a reconstituted system were able to perform the epoxidation of 1 primarily on its endocyclic double bond. The metabolites, cis- and trans-4-vinylcyclohexene 1,2-epoxide (2 and 3, respectively) and the isomeric 4-vinylcyclohexene 7,8-epoxides (4 and 5), were rapidly biotransformed into the corresponding vicinal diols by mEH-catalyzed hydrolysis. The reaction of the endocyclic epoxides occurred with good substrate diastereo- and enantio-selectivity favoring the hydrolysis of epoxides (1S,2R,4S)-3 and (1R,2S,4S)-2 to give, before 50% conversion, selectively (1R,2R,4S)-diol (6). At variance, the hydrolysis of the exocyclic epoxides was characterized by a high level of substrate enantioselection associated with a very low, if any, level of substrate diastereoselection, the two epoxides, (4R,7S)-4 and (4R,7R)-5, being hydrolyzed practically with the same rate. On the basis of the major resistance to mEH hydrolysis, the endocyclic epoxides, (1R,2S,4R)-3 and (1S,2R,4R)-2, are expected to be further oxidized, in a stereochemical manner, to the specific mutagenic diepoxides which are thought to play a crucial role in VCH ovotoxicity. Thus, VCH ovotoxicity may be markedly affected by the reactivity of the diepoxidic stereoisomers formed and detoxicated.

A stand-alone cobalt bis(dicarbollide) photoredox catalyst epoxidates alkenes in water at extremely low catalyst load

The cobalt bis(dicarbollide) complex, Na[3,3′-Co(η5-1,2-C2B9H11) (Na[1]), is an effective photoredox catalyst for the oxidation of alkenes to epoxides in water. Advantageous features of Na[1] include its lack of photoluminescence, high solubility and surfactant behavior in aqueous media, as well as the donor ability of the carborane ligand and high oxidizing power of the Co4+/3+ couple. These features differentiate it from the well-known and widely used photosensitizer tris (2,2′-bipyridine) ruthenium(ii) ([Ru(bpy)3]2+), which also participates in electron transfer through an outer sphere mechanism. A comparison of the catalytic performance of [Ru(bpy)3]2+ with Na[1] for alkene photo-oxidation is fully in favor of Na[1], as the former shows very low or null efficiency. With a catalyst loading of 0.1 mol% conversions between 65-97% have been obtained in short reaction times, 15 minutes, with moderate selectivity for the corresponding epoxide, due to the formation of side products as diols. But when the catalyst loading is reduced to 0.01 mol%, the selectivity for the corresponding epoxide increased considerably, being the only compound formed after 15 minutes of reaction (selectivity >99%). High TON values have been obtained (TON = 8500) for the epoxidation of aromatic and aliphatic alkenes in water. We have verified that Na[3,3′-Co(η5-1,2-C2B9H11)2] acts as a photocatalyst in both the epoxidation of alkenes and in their hydroxylation in aqueous medium with a higher rate for epoxidation than for hydroxylation. Preliminary photooxidation tests using methyl oleate as the substrate led to the selective epoxidation of the double bond. These results represent a promising starting point for the development of practical methods for the processing of unsaturated fatty acids, such as the valorisation of animal fat waste using this sustainable photoredox catalyst. This journal is

METHOD FOR PRODUCING EPOXY COMPOUND

The invention provides a method for producing an epoxy compound by hydrogen peroxide using an organic compound having a carbon-carbon double bond as a raw material, wherein a by-product is suppressed from being generated and the epoxy compound is produced in a high yield. In particular, the invention provides a method for producing an epoxy compound involving oxidizing a carbon-carbon double bond in an organic compound with hydrogen peroxide in the presence of a catalyst, wherein the catalyst comprises a tungsten compound; a phosphoric acid, a phosphonic acid or salts thereof; and an onium salt having an alkyl sulfate ion represented by formula (I) as an anion: wherein R1 is a linear or branched aliphatic hydrocarbon group having 1 to 18 carbons, which may be substituted with 1 to 3 phenyl groups.

Carboranycarboxylate Complexes as Efficient Catalysts in Epoxidation Reactions

This work presents the first examples of carboranylcarboxylate complexes as precatalysts in epoxidation reactions with the use of peracetic acid as the oxidant. The manganese [Mn(μ-H2O)(1-CH3-2-CO2-1,2-closo-C2B10H10)2]n·(H2O)n (1), [Mn2(1-CH3-2-CO2-1,2-closo-C2B10H10)4(2,2′-bpy)2] (2, bpy = bipyridine), [Mn(1-CH3-2-CO2-1,2-closo-C2B10H10)2(bpm)]n (3, bpm = bipyrimidine), and [Mn(1-CH3-2-CO2-1,2-closo-C2B10H10)2(2,2′-bpy)2] (4) complexes and the cobalt [Co2(μ-H2O)(1-CH3-2-CO2-1,2-closo-C2B10H10)4(thf)4] (6) complex, all containing the carboranylcarboxylic 1-CH3-2-CO2H-1,2-closo-C2B10H10 (LH) ligand, together with Mn3(OAc)6(2,2′-bpy)2 (5) displayed good performance with high conversions and selectivity values in short reaction times, in most cases. This work highlights that the coordination of the carboranylcarboxylic ligand to the metal ions is crucial to the performance of the complexes as catalysts.

Making Fe(BPBP)-catalyzed C-H and CC oxidations more affordable

The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α- [Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf) 2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C-H and C=C bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp3 C-H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude dl/meso-2,2′-bipyrrolidine. Next to its use in C-H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.

Designing the synthesis of catalytically active Ti-β by using various new templates in the presence of fluoride anion

Crystallization of large-pore Ti-β by using a variety of diquaternary ammonium derivatives of dibromoalkane and amines such as triethylamine, 1,4-diazabicyclo[2,2,2]octane (DABCO), and quinuclidine as structure-directing agents (SDA) is described. The size of hydrophobic bridging alkyl-chain length of the template [R3N+-(CH2)x-N +R3](OH-)2 directs the final crystalline product: Ti-β, Ti-ZSM-12, Ti-nonasil or Ti-ZSM-5, as x gradually changes from 6 to 1, in the fluoride medium under hydrothermal conditions. A dense phase such as Ti-nonasil (clathrasil type) is crystallized as the size of hydrophobic bridging alkyl-chain length decreases. The use of F- anions as a mineralizer and Ti4+ as a heteroatom in the synthesis gel also influences the selectivity of final crystalline product. The phase purity and incorporation of Ti4+ into the lattice of β (BEA) and ZSM-12 frameworks are confirmed using XRD, UV-visible, FT-IR, 29Si NMR spectroscopes, elemental analysis (ICP), surface area measurements and catalytic test reactions. The morphology of Ti-β samples is dependent on the nature of the structure-directing agent as revealed by the scanning electron microscopic (SEM) observations. The catalytic activity in the epoxidation of 4-vinyl-1-cyclohexene is increased with the amount of tetrahedral Ti4+ atoms in the framework. The new templates can be effectively used for preparation of catalytically active Ti-β with the minimum number of framework defect sites.

New Ru(II) complexes containing oxazoline ligands as epoxidation catalysts. Influence of the substituents on the catalytic performance

The synthesis of a family of new Ru complexes containing the facial tridentate ligand with general formula [RuII(T)(D)(X)]n+ (T = trispyrazolylmethane (tpm); D = ((4S,4′S)-(-)-4,4′,5,5′- tetrahydro-4,4′-bis(1-methylethyl)-2,2′-bioxazole) (iPr-box-C) or N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate (iPr-box-O); X = Cl, H2O) has been described. All complexes have been spectroscopically characterized in solution through 1H NMR and UV-vis techniques, and the redox properties of complexes have also been studied by means of cyclic voltammetry (CV). Furthermore, the chloro complexes presented here have been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic iPr-box-C ligand undergoes a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic ligand iPr-box-O, that keeps coordinated to the Ru metal center and that produces a strong σ-donation effect over it. The reactivity of the Ru-OH2 complexes described in this paper together with other similar ones, previously synthesized by us, has been tested with regard to the epoxidation of different olefins. Complexes [Ru II(R-box-C)(tpm)OH2](BF4)2, R = Bz, 3′c/iPr, 3c, show high stereoselectivity in the epoxidation of cis-β-methylstyrene, with the exclusive formation of the cis-epoxide. However, there is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; complex 3′c leads to the regioselective oxidation at the ring alkene position, whereas complex 3c leads to the oxidation at the terminal position. Computational calculations indicate only small energy differences between the two possible products of 4-vinylcyclohexene epoxidation, but the energy barriers for the interaction of the catalytic systems with the alkene groups of 4-vinylcyclohexene agree with the reactivity differences found for the two catalysts having isopropyl or benzyl as substituent of the oxazole ligand. Computed local Fukui functions help to explain the observed reactivity trends.

Regioselective epoxidation of different types of double bonds over large-pore titanium silicate Ti-β

Regioselective epoxidation of different types of double bonds located within the cyclic and acyclic parts of bulky olefins has been investigated using large-pore titanium silicate Ti-β in the presence of dilute aqueous H 2O2 as oxidant under mild liquid-phase conditions. Our experimental results revealed that side-chain vinylic double bonds are selectively epoxidized than those in the cyclohexene-ring. The epoxidation tendency of various bulky olefins with different positional and/or geometric isomers over Ti-β follows the order: terminal -CC- > ring -CC- ≈ bicyclic ring -CC- > allylic C - H bond. Unlike 4-vinyl-1-cyclohexene, epoxidation of an equimolar mixture of cyclohexene and 1-hexene under identical conditions using Ti-β exhibits completely different selectivity and product distributions. Steric factor and accessibility of reactants to active Ti-sites are responsible for the observed regioselectivity of bulky alkenes.

Manganese acetate in pyrrolidinium ionic liquid as a robust and efficient catalytic system for epoxidation of aliphatic terminal alkenes

Green epoxides! A novel and simple ionic liquid/manganese acetate catalytic system has been developed for the rapid and selective oxidation of aliphatic terminal alkenes to epoxides. It provides an efficient, reusable, and scalable protocol for the green synthesis of epoxides from various aliphatic terminal alkenes.