Dioxolane

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Dioxolane[1]
1,3-dioxolane-2D-skeletal.png
1,3-dioxolane-3D-balls.png
Names
IUPAC name
Dioxolane
Other names
1,3-dioxolane, formal glycol[2]
Identifiers
3D model (Jmol)
ChEBI
ChemSpider
ECHA InfoCard 100.010.422
Properties
C3H6O2
Molar mass 74.08 g/mol
Density 1.06 g/cm3
Melting point −95 °C (−139 °F; 178 K)
Boiling point 75 °C (167 °F; 348 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Dioxolane is a heterocyclic acetal with the chemical formula (CH2)2O2CH2. It is related to tetrahydrofuran by interchange of one oxygen for a CH2 group. The corresponding saturated 6-membered C4O2 rings are called dioxanes. The isomeric 1,2-dioxolane (wherein the two oxygen centers are adjacent) is a peroxide. 1,3-Dioxolane is used as a solvent and as a comonomer in polyacetals.

Dioxolanes as a class of compounds[edit]

Dioxolanes are a group of organic compounds containing the dioxolane ring. Dioxolanes can be prepared by acetalization of aldehydes and ketalization of ketones with ethylene glycol.[3]

synthesis of dioxolane group

(+)-cis-Dioxolane is the trivial name for L-(+)-cis-2-methyl-4-trimethylammoniummethyl-1,3-dioxolane iodide which is a muscarinic acetylcholine receptor agonist.

Neosporol[edit]

Neosporol is a natural product that includes a 1,3-dioxolane moiety, and is an isomer of sporol which has a 1,3-dioxane ring.[4] The total synthesis of both compounds has been reported, and each includes a step in which a dioxolane system is formed using trifluoroperacetic acid (TFPAA), prepared by the hydrogen peroxide – urea method.[5][6] This method involves no water, so it gives a completely anhydrous peracid,[7] necessary in this case as the presence of water would lead to unwanted side reactions.[5]

CF
3
COOCOCF
3
  +   H
2
O
2
•CO(NH
2
)
2
  →   CF
3
COOOH
  +   CF
3
COOH
  +   CO(NH
2
)
2

In the case of neosporol, a Prilezhaev reaction[8] with trifluoroperacetic acid is used to convert a suitable allyl alcohol precursor to an epoxide, which then undergoes a ring-expansion reaction with a proximate carbonyl functional group to form the dioxolane ring.[5][6]

Neosporol epoxidation-rearrangement.png

A similar approach is used in the total synthesis of sporol, with the dioxolane ring later expanded to a dioxane system.[4]

See also[edit]

References[edit]

  1. ^ 1,3-Dioxolane at Sigma-Aldrich
  2. ^ formal glycol - PubChem Public Chemical Database
  3. ^ R. A. Daignault, E. L. Eliel (1973). "2-Cyclohexyloxyethanol (involves acetalisation of cyclohexanone)". Org. Synth. ; Coll. Vol., 5, p. 303 
  4. ^ a b Pirrung, Michael C.; Morehead, Andrew T.; Young, Bruce G., eds. (2000). "10. Neosporol, Sporol". Part B: Bicyclic and Tricyclic Sesquiterpenes. The Total Synthesis of Natural Products. 11. John Wiley & Sons. pp. 222–224. ISBN 9780470129630. 
  5. ^ a b c Ziegler, Fredrick E.; Metcalf, Chester A.; Nangia, Ashwini; Schulte, Gayle (1993). "Structure and total synthesis of sporol and neosporol". J. Am. Chem. Soc. 115 (7): 2581–2589. doi:10.1021/ja00060a006. 
  6. ^ a b Caster, Kenneth C.; Rao, A. Somasekar; Mohan, H. Rama; McGrath, Nicholas A.; Brichacek, Matthew (2012). "Trifluoroperacetic Acid". e-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt254.pub2. 
  7. ^ Cooper, Mark S.; Heaney, Harry; Newbold, Amanda J.; Sanderson, William R. (1990). "Oxidation Reactions Using Urea–Hydrogen Peroxide; A Safe Alternative to Anhydrous Hydrogen Peroxide". Synlett. 1990 (9): 533–535. doi:10.1055/s-1990-21156. 
  8. ^ Hagen, Timothy J. (2007). "Prilezhaev reaction". In Li, Jie Jack; Corey, E. J. Name Reactions of Functional Group Transformations. John Wiley & Sons. pp. 274–281. ISBN 9780470176504. 

External links[edit]