Allyl glycidyl ether

Last updated
Allyl glycidyl ether
Strukturformel von Allylglycidylether.svg
Names
IUPAC name
2-(prop-2-enoxymethyl)oxirane
Other names
2-[(Allyloxy)methyl]oxirane
1-Allyloxy-2,3-epoxypropane
Glycidyl allyl ether
[(2-Propenyloxy)methyl] oxirane [1]
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.003.131 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-442-4
PubChem CID
UNII
  • InChI=1S/C6H10O2/c1-2-3-7-4-6-5-8-6/h2,6H,1,3-5H2
    Key: LSWYGACWGAICNM-UHFFFAOYSA-N
  • InChI=1/C6H10O2/c1-2-3-7-4-6-5-8-6/h2,6H,1,3-5H2
    Key: LSWYGACWGAICNM-UHFFFAOYAR
  • C=CCOCC1CO1
Properties
C6H10O2
Molar mass 114.144 g·mol−1
AppearanceColorless liquid [1]
Odor pleasant [1]
Density 0.97 g/mL (20 °C) [1]
Melting point −100 °C; −148 °F; 173 K [1]
Boiling point 154 °C; 309 °F; 427 K [1]
14% (20°C) [1]
Solubility in organic solvents miscible (acetone, toluene, octane) [2]
Vapor pressure 2 mmHg (20 °C) [1]
1.4348 (20 °C) [2] [3]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
poisonous, mild irritant [2]
GHS labelling:
Danger
H226, H351, H341, H332, H302, H335, H315, H318, H317, H412
Flash point 57 °C; 135 °F; 330 K [1]
Lethal dose or concentration (LD, LC):
270 ppm (mouse, 4 hr)
670 ppm (rat, 8 hr) [4]
NIOSH (US health exposure limits):
PEL (Permissible)
10 ppm (45 mg/m3) [1]
REL (Recommended)
TWA 5 ppm (22 mg/m3) ST 10 ppm (44 mg/m3) [skin] [1]
IDLH (Immediate danger)
50 ppm [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Allyl glycidyl ether is an organic compound used in adhesives and sealants and as a monomer for polymerization reactions. It is formally the condensation product of allyl alcohol and glycidol via an ether linkage. Because it contains both an alkene and an epoxide group, either group can be reacted selectively to yield a product where the other functional group remains intact for future reactions.

Contents

Preparation

AGE is prepared commercially by the etherification of allyl alcohol with epichlorohydrin. Hydrogen chloride, the byproduct of their condensation, is removed with a base. [5]

The synthesis of allyl glycidyl ether by condensation of allyl alcohol and epichlorohydrin Ubersichtsreaktion Allylglycidylether.svg
The synthesis of allyl glycidyl ether by condensation of allyl alcohol and epichlorohydrin

AGE can also be synthesized by monoepoxidation of diallyl ether. [6] [7]

The synthesis of allyl glycidyl ether by epoxidation of diallyl ether Diallyl ether epoxidation.png
The synthesis of allyl glycidyl ether by epoxidation of diallyl ether

Diepoxidation of the second alkene would produce diglycidyl ether.

Allyl glycidyl ether is chiral. Most routes yield a racemic mixture. Epoxidation using monooxygenase enzyme proceeds enantioselectively. [8]

The enantioselective synthesis of allyl glycidyl ether by microbial epoxidation of diallyl ether Diallyl ether microbial epoxidation.png
The enantioselective synthesis of allyl glycidyl ether by microbial epoxidation of diallyl ether

Alternately, nucleophilic cyclization of either chirality of the secondary alcohol onto a primary tosylate gives the chiral epoxide product. [9]

The synthesis of a single enantiomer of allyl glycidyl ether by cyclization of a single enantiomer of the acylic alcohol Chiral allyl glyclidyl ether by SN2.png
The synthesis of a single enantiomer of allyl glycidyl ether by cyclization of a single enantiomer of the acylic alcohol

Uses

Allyl glycidyl ether is used in adhesives and sealants [2] and as a monomer for various types of polymer preparations.

Reactions

Polymerization

As a bifunctional compound, the alkene group or the epoxide group can be reacted selectively to yield a product where the other functional group remains intact for future reactions. For example, either one of them could be used for linear polymerization, and then the other used for cross-linking. [6]

Radical polymerization of the propylene portion in the presence of methyl acrylate yields a block copolymer with a high epoxide content. [10] Similarly, it is can be used in the production of polyvinylcaprolactam as a chain transfer agent. [11]

Nucleophilic polymerization of the epoxide groups gives a material that has the same backbone as polyethylene glycol, with allyl-ether side chains. The additional Lewis basic ether sites alter ion transport in the polymer and also affect the transient inter-chain crosslinking and glass transition temperature in the presence of metal ions. These properties suggest that the material may have applications as an alternative electrolyte for lithium-ion batteries. The alkenes can be elaborated into short polyethylene-glycol oligomers to further increase the ion-binding ability and enhance the resulting material properties. [12]

Block copolymers with ethylene oxide form micelles, which could be useful for encapsulating other molecules as part of a drug delivery system. The alkenes of these macromolecular structures can also be cross-linked via radical polymerization. [13]

Lewis-acid-catalyzed co-polymerisation with carbon dioxide likewise gives a polycarbonate material with allyl side chains that can be further elaborated. [14]

Hydrosilylation

Rather than polymerization, the alkene group can undergo a hydrosilylation reaction with siloxanes in the presence of chloroplatinic acid as catalyst. [15] Like the polymerization reactions, this reaction also leaves the epoxide intact. By this reaction, allyl glycidyl ether finds use as an intermediate in the production of silane coatings for electrical applications. [16]

See also

Related Research Articles

<span class="mw-page-title-main">Sharpless epoxidation</span> Chemical reaction

The Sharpless epoxidation reaction is an enantioselective chemical reaction to prepare 2,3-epoxyalcohols from primary and secondary allylic alcohols. The oxidizing agent is tert-butyl hydroperoxide. The method relies on a catalyst formed from titanium tetra(isopropoxide) and diethyl tartrate.

<span class="mw-page-title-main">Epoxy</span> Type of material

Epoxy is the family of basic components or cured end products of epoxy resins. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. The epoxide functional group is also collectively called epoxy. The IUPAC name for an epoxide group is an oxirane.

<span class="mw-page-title-main">Epoxide</span> Organic compounds with a carbon-carbon-oxygen ring

In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides 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.

A diol is a chemical compound containing two hydroxyl groups. An aliphatic diol is also called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified.

<span class="mw-page-title-main">Allyl alcohol</span> Organic compound (CH2=CHCH2OH)

Allyl alcohol is an organic compound with the structural formula CH2=CHCH2OH. Like many alcohols, it is a water-soluble, colourless liquid. It is more toxic than typical small alcohols. Allyl alcohol is used as a precursor to many specialized compounds such as flame-resistant materials, drying oils, and plasticizers. Allyl alcohol is the smallest representative of the allylic alcohols.

<span class="mw-page-title-main">Jacobsen epoxidation</span>

The Jacobsen epoxidation, sometimes also referred to as Jacobsen-Katsuki epoxidation is a chemical reaction which allows enantioselective epoxidation of unfunctionalized alkyl- and aryl- substituted alkenes. It is complementary to the Sharpless epoxidation (used to form epoxides from the double bond in allylic alcohols). The Jacobsen epoxidation gains its stereoselectivity from a C2 symmetric manganese(III) salen-like ligand, which is used in catalytic amounts. The manganese atom transfers an oxygen atom from chlorine bleach or similar oxidant. The reaction takes its name from its inventor, Eric Jacobsen, with Tsutomu Katsuki sometimes being included. Chiral-directing catalysts are useful to organic chemists trying to control the stereochemistry of biologically active compounds and develop enantiopure drugs.

<span class="mw-page-title-main">Johnson–Corey–Chaykovsky reaction</span> Chemical reaction in organic chemistry

The Johnson–Corey–Chaykovsky reaction is a chemical reaction used in organic chemistry for the synthesis of epoxides, aziridines, and cyclopropanes. It was discovered in 1961 by A. William Johnson and developed significantly by E. J. Corey and Michael Chaykovsky. The reaction involves addition of a sulfur ylide to a ketone, aldehyde, imine, or enone to produce the corresponding 3-membered ring. The reaction is diastereoselective favoring trans substitution in the product regardless of the initial stereochemistry. The synthesis of epoxides via this method serves as an important retrosynthetic alternative to the traditional epoxidation reactions of olefins.

<span class="mw-page-title-main">Epichlorohydrin</span> Chemical compound

Epichlorohydrin is an organochlorine compound and an epoxide. Despite its name, it is not a halohydrin. It is a colorless liquid with a pungent, garlic-like odor, moderately soluble in water, but miscible with most polar organic solvents. It is a chiral molecule generally existing as a racemic mixture of right-handed and left-handed enantiomers. Epichlorohydrin is a highly reactive electrophilic compound and is used in the production of glycerol, plastics, epoxy glues and resins, epoxy diluents and elastomers.

In organic chemistry, kinetic resolution is a means of differentiating two enantiomers in a racemic mixture. In kinetic resolution, two enantiomers react with different reaction rates in a chemical reaction with a chiral catalyst or reagent, resulting in an enantioenriched sample of the less reactive enantiomer. As opposed to chiral resolution, kinetic resolution does not rely on different physical properties of diastereomeric products, but rather on the different chemical properties of the racemic starting materials. The enantiomeric excess (ee) of the unreacted starting material continually rises as more product is formed, reaching 100% just before full completion of the reaction. Kinetic resolution relies upon differences in reactivity between enantiomers or enantiomeric complexes.

<span class="mw-page-title-main">Glycidol</span> Chemical compound

Glycidol is an organic compound that contains both epoxide and alcohol functional groups. Being bifunctional, it has a variety of industrial uses. The compound is a slightly viscous liquid that is slightly unstable and is not often encountered in pure form.

<span class="mw-page-title-main">Jacobsen's catalyst</span> Chemical compound

Jacobsen's catalyst is the common name for N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane­diaminomanganese(III) chloride, a coordination compound of manganese and a salen-type ligand. It is used as an asymmetric catalyst in the Jacobsen epoxidation, which is renowned for its ability to enantioselectively transform prochiral alkenes into epoxides. Before its development, catalysts for the asymmetric epoxidation of alkenes required the substrate to have a directing functional group, such as an alcohol as seen in the Sharpless epoxidation. This compound has two enantiomers, which give the appropriate epoxide product from the alkene starting material.

2-Ethylhexyl glycidyl ether is a liquid organic molecule with formula C11H22O2 an industrial chemical used to reduce the viscosity of epoxy resins. These are then used in adhesives, sealants, and paints or coatings. It has the CAS Registry Number of 2461-15-6. It has the IUPAC name of 2-(2-ethylhexoxymethyl)oxirane. It also finds use in other polymer based applications.

<i>o</i>-Cresyl glycidyl ether Chemical compound

o-Cresyl glycidyl ether (ortho-cresyl glycidyl ether, o-CGE) is a liquid aromatic organic chemical compound and chemically a glycidyl ether. It has the formula C10H12O2 and the CAS Registry Number 2210-79-9. It is one of a number of glycidyl ethers available commercially that are used to reduce the viscosity of epoxy resins. These are then further used in coatings, sealants, adhesives and elastomers.

Neopentyl glycol diglycidyl ether (NPGDGE) is an organic chemical in the glycidyl ether family. It is aliphatic and a colorless liquid. It has the formula C11H20O4 and the CAS registry number of 17557-23-2. It has two oxirane groups per molecule. Its principle use is in modifying epoxy resins.

1,6-Hexanediol diglycidyl ether is an organic chemical in the glycidyl ether family. It is an aliphatic compound that is a colorless liquid. It has two epoxide (oxirane) groups per molecule. Its main use is in modifying epoxy resins especially viscosity reduction whilst flexibilizing. It is REACH registered.

<span class="mw-page-title-main">C12–C14 alcohol glycidyl ether</span> Chemical compound

C12-C14 alcohol glycidyl ether (AGE) is an organic chemical in the glycidyl ether family. It is a mixture of mainly 12 and 14 carbon chain alcohols, also called fatty alcohols that have been glycidated. It is an industrial chemical used as a surfactant but primarily for epoxy resin viscosity reduction. It has the CAS number 68609-97-2 but the IUPAC name is more complex as it is a mixture and is 2-(dodecoxymethyl)oxirane;2-(tetradecoxymethyl)oxirane;2-(tridecoxymethyl)oxirane. Other names include dodecyl and tetradecyl glycidyl ethers and alkyl (C12-C14) glycidyl ether.

<span class="mw-page-title-main">Castor oil glycidyl ether</span> Chemical compound

Castor oil glycidyl ether is a liquid organic chemical in the glycidyl ether family. It is sometimes called castor oil triglycidyl ether. It has the theoretical formula C66H116O12 and the CAS number 14228-73-0. The IUPAC name is 2,3-bis[12-(oxiran-2-ylmethoxy)octadec-9-enoyloxy]propyl 12-(oxiran-2-ylmethoxy)octadec-9-enoate. A key use is acting as a modifier for epoxy resins as a reactive diluent that adds flexibility and improved mechanical properties.

<span class="mw-page-title-main">C12–C13 alcohol glycidyl ether</span> Chemical compound

C12-C13 alcohol glycidyl ether is a mixture of organic chemicals in the glycidyl ether family. It is a mixture of mainly 12 and 13 carbon chain alcohols, also called fatty alcohols that have been glycidated. It is an industrial chemical used as a surfactant but primarily for epoxy resin viscosity reduction. It has the CAS number 120547-52-6.

<span class="mw-page-title-main">Diethylene glycol diglycidyl ether</span> Chemical compound

Diethylene glycol diglycidyl ether (DEGDGE) is an organic chemical in the glycidyl ether family with the formula C10H18O5.. The oxirane functionality makes it useful as a reactive diluent for epoxy resin viscosity reduction.

<span class="mw-page-title-main">Phenyl glycidyl ether</span> Chemical compound

Phenyl glycidyl ether, is a liquid aromatic organic chemical in the glycidyl ether class of compounds. It has the formula C9H10O2. It has the CAS Registry Number 122-60-1 and the IUPAC name of 2-(phenoxymethyl)oxirane. A key use is in the viscosity reduction of epoxy resin systems. It is REACH registered and on EINECS under the name 2,3-epoxypropyl phenyl ether.

References

  1. 1 2 3 4 5 6 7 8 9 10 11 12 NIOSH Pocket Guide to Chemical Hazards. "#0019". National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 3 4 CID 7838 from PubChem
  3. ↑ Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982., p. 2199
  4. ↑ "Allyl glycidyl ether". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  5. ↑ Clayton, G. D.; Clayton, F. E., eds. (1981–1982). Patty's Industrial Hygiene and Toxicology. Vol. 2A, 2B, 2C: Toxicology (3rd ed.). New York: John Wiley Sons. p. 2197.
  6. 1 2 Frostick, Frederick C. Jr.; Phillips, Benjamin; Starcher, Paul S. (1959). "Synthesis of Some Epoxy Vinyl Monomers by Epoxidation with Peracetic Acid". J. Am. Chem. Soc. 81 (13): 3350–3356. doi:10.1021/ja01522a048.
  7. ↑ Wróblewska, Agnieszka; Drewnowska, E.; Gawarecka, A. (August 2016). "The epoxidation of diallyl ether to allyl-glycidyl ether over the TS-1 catalyst". Reaction Kinetics, Mechanisms and Catalysis. 118 (2): 719–931. doi:10.1007/s11144-016-1028-3. S2CID   101802831.
  8. ↑ Fu, Hong; Newcomb, Martin; Wong, Chi Huey (1991). "Pseudomonas oleovorans monooxygenase-catalyzed asymmetric epoxidation of allyl alcohol derivatives and hydroxylation of a hypersensitive radical probe with the radical ring-opening rate exceeding the oxygen-rebound rate". J. Am. Chem. Soc. 113 (15): 5878–5880. doi:10.1021/ja00015a061.
  9. ↑ Pederson, Richard L.; Liu, Kevin K. C.; Rutan, James F.; Chen, Lihren; Wong, Chi Huey (1990). "Enzymes in organic synthesis: synthesis of highly enantiomerically pure 1,2-epoxy aldehydes, epoxy alcohols, thiirane, aziridine, and glyceraldehyde 3-phosphate". J. Org. Chem. 55 (16): 4897–4901. doi:10.1021/jo00303a026.
  10. ↑ Qingbo, Yu; Mingxu, Zhang; Xianhua, Li; Ruke, Bai (October 2007). "Living free-radical copolymerization of allyl glycidyl ether with methyl acrylate". Frontiers of Chemistry in China. 2 (4): 414–418. doi:10.1007/s11458-007-0078-5. S2CID   195308634.
  11. ↑ Kudyshkin, Mukhitdinova (1999). "Control of the molecular weight of polyvinylcaprolactam". Russian Journal of Applied Chemistry. 72 (10): 1846–1848.
  12. ↑ Barteau, Katherine P.; Wolffs, Martin; Lynd, Nathaniel A.; Fredrickson, Glenn H.; Kramer, Edward J.; Hawker, Craig J. (2013). "Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries". Macromolecules. 46 (22): 8988–8994. Bibcode:2013MaMol..46.8988B. doi:10.1021/ma401267w.
  13. ↑ Hrubý, M.; Koňák, Č.; Ulbrich, K. (2004). "Poly(allyl glycidyl ether)-block-poly(ethylene oxide): A novel promising polymeric intermediate for the preparation of micellar drug delivery systems". Journal of Applied Polymer Science. 95 (2): 201–211. doi:10.1002/app.21121.
  14. ↑ Łukaszczyk, Jan; Jaszcz, Katarzyna; Kuran, Witold; Listos, Tomasz (2000). "Synthesis of functional polycarbonates by copolymerization of carbon dioxide with allyl glycidyl ether". Macromolecular Rapid Communications. 21 (11): 754–757. doi:10.1002/1521-3927(20000701)21:11<754::AID-MARC754>3.0.CO;2-O.
  15. ↑ "Allyl glycidyl ether". Sigma-Aldrich . Retrieved December 24, 2018.
  16. ↑ Ash, Michael; Ash, Irene, eds. (2007). Handbook of Fillers, Extenders, and Diluents. Synapse Info Resources. p. 224. ISBN   9781890595968.
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