This article is about 1,3-dioxolane. For the other dioxolane isomer, see
1,2-dioxolane .
Dioxolane
[1]
Names
Preferred IUPAC name
Systematic IUPAC name
Other names
Dioxolane
5-Crown-2
Formal glycol
[2]
Identifiers
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
100.010.422
EC Number
UNII
UN number
1166
InChI=1S/C3H6O2/c1-2-4-5-3-1/h1-3H2
Y Key: SNQXJPARXFUULZ-UHFFFAOYSA-N
Y InChI=1/C3H6O2/c1-2-4-5-3-1/h1-3H2
Key: SNQXJPARXFUULZ-UHFFFAOYAS
Properties
C3 H6 O2
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)
Hazards
GHS labelling :
[4]
Danger
H225
P210 ,
P233 ,
P240 ,
P241 ,
P242 ,
P243 ,
P280 ,
P303+P361+P353 ,
P370+P378 ,
P403+P235 ,
P501
Except where otherwise noted, data are given for materials in their
standard state (at 25 °C [77 °F], 100 kPa).
Chemical compound
Dioxolane is a
heterocyclic
acetal with the
chemical formula (CH2 )2 O2 CH2 . It is related to
tetrahydrofuran (THF) by replacement of the
methylene group (CH2 ) at the 2-position with an oxygen atom. The corresponding saturated 6-membered C4 O2 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 co
monomer in
polyacetals .
As a class of compounds
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 .
[5]
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 .
Protecting groups
Organic compounds containing
carbonyl groups sometimes need
protection so that they do not undergo reactions during transformations of other
functional groups that may be present. A variety of approaches to protection and deprotection of carbonyls
[6] including as dioxolanes
[7] are known. For example, consider the compound methyl cyclohexanone-4-carboxylate, where
lithium aluminium hydride reduction will produce 4-hydroxymethylcyclohexanol. The ester functional group can be reduced without affecting the
ketone by protecting the ketone as a
ketal . The ketal is produced by acid catalysed reaction with
ethylene glycol , the reduction reaction carried out, and the protecting group removed by hydrolysis to produce 4-hydroxymethylcyclohexanone.
NaBArF4 can also be used for deprotection of acetal or ketal-protected carbonyl compounds.
[6]
[7] For example, deprotection of 2-phenyl-1,3-dioxolane to
benzaldehyde can be achieved in water in five minutes at 30 °C.
[8]
PhCH(OCH2 )2 +
H2 O
→
30 °C / 5 min
NaBAr
4
{\displaystyle {\ce {->[{\ce {NaBAr4}}][{\text{30 °C / 5 min}}]}}}
PhCHO +
HOCH2 CH2 OH
Natural products
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.
[9] 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.
[10]
[11] This method involves no water, so it gives a completely
anhydrous peracid,
[12] necessary in this case as the presence of water would lead to unwanted
side reactions .
[10]
CF3 COOCOCF3 +
H2 O2 •CO(NH2 )2 →
CF3 COOOH +
CF3 COOH +
CO(NH2 )2
In the case of neosporol, a
Prilezhaev reaction
[13] 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.
[10]
[11]
A similar approach is used in the total synthesis of sporol, with the dioxolane ring later expanded to a dioxane system.
[9]
See also
References
^
1,3-Dioxolane at
Sigma-Aldrich
^
formal glycol - PubChem Public Chemical Database
^ "Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) . Cambridge:
The Royal Society of Chemistry . 2014. p. 145.
doi :
10.1039/9781849733069-FP001 .
ISBN
978-0-85404-182-4 .
^
"1,3-Dioxolane" . pubchem.ncbi.nlm.nih.gov .
^ R. A. Daignault, E. L. Eliel (1973).
"2-Cyclohexyloxyethanol (involves acetalisation of cyclohexanone)" .
Organic Syntheses ; Collected Volumes , vol. 5, p. 303 .
^
a
b Greene, Theodora W.; Wuts, Peter G. M. (1999). "Dimethyl acetals".
Greene's Protective Groups in Organic Synthesis (3rd ed.).
Wiley-Interscience . pp. 297–304, 724–727.
ISBN
9780471160199 .
Archived from the original on December 3, 2016. Retrieved June 20, 2017 .
^
a
b Greene, Theodora W.; Wuts, Peter G. M. (1999). "1,3-Dioxanes, 1,3-Dioxolanes".
Greene's Protective Groups in Organic Synthesis (3rd ed.).
Wiley-Interscience . pp. 308–322, 724–727.
ISBN
9780471160199 .
Archived from the original on December 7, 2016. Retrieved June 20, 2017 .
^ Chang, Chih-Ching; Liao, Bei-Sih; Liu, Shiuh-Tzung (2007). "Deprotection of Acetals and Ketals in a Colloidal Suspension Generated by Sodium Tetrakis(3,5-trifluoromethylphenyl)borate in Water".
Synlett . 2007 (2): 283–287.
doi :
10.1055/s-2007-968009 .
^
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. Vol. 11.
John Wiley & Sons . pp. 222–224.
ISBN
9780470129630 .
^
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 .
^
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 .
ISBN
978-0471936237 .
^ 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 .
^ Hagen, Timothy J. (2007).
"Prilezhaev reaction" . In Li, Jie Jack;
Corey, E. J. (eds.). Name Reactions of Functional Group Transformations .
John Wiley & Sons . pp. 274–281.
ISBN
9780470176504 .
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