Cyclohexene oxide

Last updated
Cyclohexene oxide
Cyclohexeenoxide.png
Names
IUPAC name
7-Oxabicyclo[4.1.0]heptane
Other names
Epoxycyclohexane
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.005.462 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C6H10O/c1-2-4-6-5(3-1)7-6/h5-6H,1-4H2
    Key: ZWAJLVLEBYIOTI-UHFFFAOYSA-N
  • C1CCC2C(C1)O2
Properties
C6H10O
Molar mass 98.145 g·mol−1
AppearanceColorless liquid [1]
Density 0.97 g·cm−3 [1]
Melting point ca. -40 °C [1]
Boiling point ca. 130 °C [1]
Practically insoluble [1]
Vapor pressure 12 mbar (at 20 °C) [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Cyclohexene oxide is a cycloaliphatic epoxide. It can react in cationic polymerization to poly(cyclohexene oxide). As cyclohexene is monovalent, poly(cyclohexene oxide) is a thermoplastic.

Contents

Production

Cyclohexene oxide is produced in epoxidation reaction from cyclohexene. The epoxidation can take place either in a homogeneous reaction by peracids [2] or heterogeneous catalysis (e.g. silver and molecular oxygen). [3] [4] [5]

Cyclohexeenoxide-synthese.png

In industrial production the heterogeneously catalyzed synthesis is preferred because of better atom economy, a simpler separation of the product and easier recycling of catalyst. A short overview and an investigation of the oxidation of cyclohexene by hydrogen peroxide is given in the literature. [6] In recent times the catalytic oxidation of cyclohexene by (immobilized) metalloporphyrin complexes has been found to be an efficient way. [7] [8]

In laboratory, cyclohexene oxide can also be prepared by reacting cyclohexene with magnesium monoperoxyphthalate (MMPP) in a mixture of isopropanol and water as solvent at room temperature. [9]

Synthesis of cyclohexene oxide.svg

With this method, good yields up to 85 % can be reached.

Properties and reactions

Cyclohexene has been studied extensively by analytical methods. [10] Cyclohexene oxide can be polymerized in solution, catalyzed by a solid acid catalyst. [11]

Application

One of the known uses is in the synthesis of bromadoline.

Related Research Articles

Catalysis Process of increasing the rate of a chemical reaction

Catalysis is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst. Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process regenerating the catalyst.

Sharpless epoxidation

The Sharpless epoxidation reaction is an enantioselective chemical reaction to prepare 2,3-epoxyalcohols from primary and secondary allylic alcohols.

Hydrogenation Chemical reaction between molecular hydrogen and another compound or element

Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically constitutes the addition of pairs of hydrogen atoms to a molecule, often an alkene. Catalysts are required for the reaction to be usable; non-catalytic hydrogenation takes place only at very high temperatures. Hydrogenation reduces double and triple bonds in hydrocarbons.

Epoxide

An epoxide is a cyclic ether with a three-atom ring. This ring approximates an equilateral triangle, which makes it strained, and hence highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.

Hydrogen peroxide - urea Chemical compound

Hydrogen peroxide - urea is a solid composed of equal amounts of hydrogen peroxide and urea. This compound is a white crystalline solid which dissolves in water to give free hydrogen peroxide. Hydrogen peroxide - urea contains solid and water-free hydrogen peroxide, which offers a higher stability and better controllability than liquid hydrogen peroxide when used as an oxidizing agent. Often called carbamide peroxide in the dental office, it is used as a source of hydrogen peroxide for bleaching, disinfection, and oxidation.

Cyclohexene is a hydrocarbon with the formula C6H10. This cycloalkene is a colorless liquid with a sharp smell. It is an intermediate in various industrial processes. Cyclohexene is not very stable upon long term storage with exposure to light and air because it forms peroxides.

Dehydrogenation is the a chemical reaction that involves the removal of hydrogen, usually from an organic molecule. It is the reverse of hydrogenation. Dehydrogenation is important, both as a useful reaction and a serious problem. At its simplest, it is useful way of converting alkanes, which are relatively inert and thus low-valued, to olefins, which are reactive and thus more valuable. Alkenes are precursors to aldehydes, alcohols, polymers, and aromatics. As a problematic reaction, the fouling and inactivation of many catalysts arises via coking, which is the dehydrogenative polymerization of organic substrates.

Hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the production of aldehydes from alkenes. This chemical reaction entails the net addition of a formyl group (CHO) and a hydrogen atom to a carbon-carbon double bond. This process has undergone continuous growth since its invention: Production capacity reached 6.6×106 tons in 1995. It is important because aldehydes are easily converted into many secondary products. For example, the resulting aldehydes are hydrogenated to alcohols that are converted to detergents. Hydroformylation is also used in speciality chemicals, relevant to the organic synthesis of fragrances and drugs. The development of hydroformylation is one of the premier achievements of 20th-century industrial chemistry.

In chemistry, homogeneous catalysis is catalysis in a solution by a soluble catalyst. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysis describes processes where the catalysts and substrate are in distinct phases, typically solid-gas, respectively. The term is used almost exclusively to describe solutions and implies catalysis by organometallic compounds. Homogeneous catalysis is established technology that continues to evolve. An illustrative major application is the production of acetic acid. Enzymes are examples of homogeneous catalysts.

The Tishchenko reaction is an organic chemical reaction that involves disproportionation of an aldehyde in the presence of an alkoxide. The reaction is named after Russian organic chemist Vyacheslav Tishchenko, who discovered that aluminium alkoxides are effective catalysts for the reaction.

(<i>E</i>)-Stilbene Chemical compound

(E)-Stilbene, commonly known as trans-stilbene, is an organic compound represented by the condensed structural formula C6H5CH=CHC6H5. Classified as a diarylethene, it features a central ethylene moiety with one phenyl group substituent on each end of the carbon–carbon double bond. It has an (E) stereochemistry, meaning that the phenyl groups are located on opposite sides of the double bond, the opposite of its geometric isomer, cis-stilbene. Trans-stilbene occurs as a white crystalline solid at room temperature and is highly soluble in organic solvents. It can be converted to cis-stilbene photochemically, and further reacted to produce phenanthrene.

Pivalic acid is a carboxylic acid with a molecular formula of (CH3)3CCO2H. This colourless, odiferous organic compound is solid at room temperature. A common abbreviation for the pivalyl or pivaloyl group (t-BuC(O)) is Piv and for pivalic acid (t-BuC(O)OH) is PivOH.

Organocatalysis Method in organic chemistry

In organic chemistry, organocatalysis is a form of catalysis in which the rate of a chemical reaction is increased by an organic catalyst. This "organocatalyst" consists of carbon, hydrogen, sulfur and other nonmetal elements found in organic compounds. Because of their similarity in composition and description, they are often mistaken as a misnomer for enzymes due to their comparable effects on reaction rates and forms of catalysis involved.

Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

In nitrile reduction a nitrile is reduced to either an amine or an aldehyde with a suitable chemical reagent.

DuPhos

DuPhos is a class of organophosphorus compound that are used ligands for asymmetric synthesis. The name DuPhos is derived from (1) the chemical company that sponsored the research leading to this ligand's invention, DuPont and (2) the compound is a diphosphine ligand type. Specifically it is classified as a C2-symmetric ligand, consisting of two phospholanes rings affixed to a benzene ring.

Nucleophilic epoxidation is the formation of epoxides from electron-deficient double bonds through the action of nucleophilic oxidants. Nucleophilic epoxidation methods represent a viable alternative to electrophilic methods, many of which do not epoxidize electron-poor double bonds efficiently.

Catalyst support Porous material with a high specific surface area supporting a catalyst

In chemistry, a catalyst support is the material, usually a solid with a high surface area, to which a catalyst is affixed. The activity of heterogeneous catalysts is mainly promoted by atoms present at the accessible surface of the material. Consequently, great effort is made to maximize the specific surface area of a catalyst. One popular method for increasing surface area involves distributing the catalyst over the surface of the support. The support may be inert or participate in the catalytic reactions. Typical supports include various kinds of carbon, alumina, and silica.

The Juliá–Colonna epoxidation is an asymmetric poly-leucine catalyzed nucleophilic epoxidation of electron deficient olefins in a triphasic system. The reaction was reported by Sebastian Juliá at the Chemical Institute of Sarriá in 1980, with further elaboration by both Juliá and Stefano Colonna.

<i>tert</i>-Butyl peroxybenzoate Chemical compound

tert-Butyl peroxybenzoate (TBPB) a chemical compound from the group of peresters (compounds containing the general structure R1-C(O)OO-R2) which contains a phenyl group as R1 and a tert-butyl group as R2. It is often used as a radical initiator in polymerization reactions, such as the production of LDPE from ethylene, and for crosslinking, such as for unsaturated polyester resins.

References

  1. 1 2 3 4 5 6 Record of Epoxycyclohexane in the GESTIS Substance Database of the Institute for Occupational Safety and Health, accessed on 1 February 2014.
  2. M. Quenard; V. Bonmarin; G. Gelbard (1987). "Epoxidation of olefins by hydrogen peroxide catalyzed by phosphonotungstic complexes". Tetrahedron Letters. 28 (20): 2237–2238. doi:10.1016/S0040-4039(00)96089-1.
  3. Ha Q. Pham; Maurice J. Marks (2005), "Epoxy Resins", Ullmann's Encyclopedia of Industrial Chemistry (in German), doi:10.1002/14356007.a09_547.pub2, ISBN   3527306730
  4. Siegfried Rebsdat; Dieter Mayer (2001), "Ethylene Oxide", Ullmann's Encyclopedia of Industrial Chemistry (in German), doi:10.1002/14356007.a10_117, ISBN   3527306730
  5. "Spectroscopic investigation of the molybdenum active sites on MoVI heterogeneous catalysts for alkene epoxidation". Journal of the Chemical Society, Faraday Transactions. 1995. doi:10.1039/FT9959103969.
  6. Ambili, V K; Dr.Sugunan, S, Faculty of Sciences (ed.), Studies on Catalysis by Ordered Mesoporous SBA-15 Materials Modified with Transition Metals (in German), retrieved 2014-07-27CS1 maint: multiple names: authors list (link)
  7. Costa, Andréia A. Ghesti; Grace F. de Macedo; Julio L. Braga; Valdeilson S. Santos; Marcello M. Dias; José A. Dias; Sílvia C.L. (2008). "Immobilization of Fe, Mn and Co tetraphenylporphyrin complexes in MCM-41 and their catalytic activity in cyclohexene oxidation reaction by hydrogen peroxide". Journal of Molecular Catalysis A: Chemical. 282 (1–2): 149–157. doi:10.1016/j.molcata.2007.12.024.
  8. Xian-Tai Zhou; Hong-Bing Ji; Jian-Chang Xu; Li-Xia Pei; Le-Fu Wang; Xing-Dong Yao (2007). "Enzymatic-like mediated olefins epoxidation by molecular oxygen under mild conditions". Tetrahedron Letters. 48 (15): 2691–2695. doi:10.1016/j.tetlet.2007.02.066.
  9. Brougham, Paul; Cooper, Mark S.; Cummerson, David A.; Heaney, Harry; Thompson, Nicola (1987). "Oxidation Reactions Using Magnesium Monoperphthalate: A Comparison with m-Chloroperoxybenzoic Acid". Synthesis. 1987 (11): 1015–1017. doi:10.1055/s-1987-28153 . Retrieved 2020-07-31.
  10. RM Ibberson; O. Yamamuro; I. Tsukushi (2006). "The crystal structures and phase behaviour of cyclohexene oxide". Chemical Physics Letters. 423 (4–6): 454–458. Bibcode:2006CPL...423..454I. doi:10.1016/j.cplett.2006.04.004.
  11. Ahmed Yahiaoui; Mohammed Belbachir; Jeanne Claude Soutif; Laurent Fontaine (2005). "Synthesis and structural analyses of poly(1,2-cyclohexene oxide) over solid acid catalyst". Materials Letters. 59 (7): 759–767. doi:10.1016/j.matlet.2004.11.017.