Selective synthesis and stabilization of peroxides: Via phosphine oxides

Article abstract of DOI:10.1039/c9nj04858h

Reaction of bis(dicyclohexylphosphino)ethane dioxide with hydrogen peroxide leads to an extended crystalline network based on the formation of hydrogen bonds with the PO groups of the diphosphine dioxide. The structural motif of the network is characterized by X-ray diffraction. A new selective synthesis for an industrially important MEKPO (methyl ethyl ketone peroxide) dimer is described. The dimer is created by reaction of dppe dioxide (bis(diphenylphosphino)ethane dioxide) with butanone and hydrogen peroxide. This peroxide is stabilized by forming strong hydrogen bonds to the phosphine oxide groups within an extended network, which has been characterized by single crystal X-ray diffraction. Reaction of acetylacetone with hydrogen peroxide, irrespective of the presence of phosphine oxide, leads to the stereoselective formation of two dioxolanes. Both cyclic peroxides have been obtained in crystalline forms suitable for single crystal X-ray diffractions.

Full text of DOI:10.1039/c9nj04858h

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Selective synthesis and stabilization of peroxides
via phosphine oxides†
Cite this: New J. Chem., 2019,
43, 17174
Fabian F. Arp, Shin Hye Ahn, Nattamai Bhuvanesh and Janet Blumel
*
¨
Reaction of bis(dicyclohexylphosphino)ethane dioxide with hydrogen peroxide leads to an extended
crystalline network based on the formation of hydrogen bonds with the PQO groups of the diphosphine
dioxide. The structural motif of the network is characterized by X-ray diffraction. A new selective
synthesis for an industrially important MEKPO (methyl ethyl ketone peroxide) dimer is described. The
dimer is created by reaction of dppe dioxide (bis(diphenylphosphino)ethane dioxide) with butanone and
hydrogen peroxide. This peroxide is stabilized by forming strong hydrogen bonds to the phosphine
oxide groups within an extended network, which has been characterized by single crystal X-ray
diffraction. Reaction of acetylacetone with hydrogen peroxide, irrespective of the presence of phosphine
oxide, leads to the stereoselective formation of two dioxolanes. Both cyclic peroxides have been
obtained in crystalline forms suitable for single crystal X-ray diffractions.
Received 25th September 2019,
Accepted 21st October 2019
DOI: 10.1039/c9nj04858h
rsc.li/njc
phosphine oxides to create extended hydrogen-bonded net-
works.12,13 Furthermore, hydrogen bonding with naphthol,14
Introduction
Phosphine oxides are compounds that have been described in sulfonic acids,15 and water has been reported.8,16–18 Even silanols,
inorganic chemistry textbooks for a long time. Recently, they phenols, and chloroform crystallize as hydrogen-bonded
came back into the spotlight in many different areas. They are, assemblies.19 Besides single crystal X-ray diffraction, 31P solid-
for example, unwanted byproducts of phosphine coordination state NMR spectroscopy is a powerful method to analyze the
chemistry, especially in the field of immobilized catalysts.1–4 hydrogen bonding characteristics of diverse P(V) species.8–10,17,20
Many linkers that are used to tether metal complexes to solid
We discovered recently that phosphine oxides are also able
oxide supports contain phosphine groups. Once the latter are to stabilize hydrogen peroxide and di(hydroperoxy)alkanes by
oxidized to phosphine oxides, the catalyst is no longer retained forming hydrogen bonds.17,18,21–23 The Hilliard adducts can be
and leaches from the support.5 Furthermore, phosphine oxides generated by exposing phosphines or phosphine oxides to
are co-products of Wittig and Appel reactions. In another field, aqueous H2O2. They exhibit most commonly the structural
they are applied to probe surface acidities6 and recently became motifs (R3POꢀH2O2)2 or (R3PO)2ꢀH2O2.21–23 Ahn adducts form
the focus of attention regarding the decomposition of warfare assemblies of the type R3POꢀ(HOO)2CR0R00 (R, R0, R00 = alkyl and
agents.7 In this context, phosphine oxides have been shown to aryl) when phosphines, their oxides, or Hilliard adducts are
be very mobile on surfaces, which leads to interesting line- reacted with ketones in the presence of aqueous H2O2.21–23
narrowing effects in the 31P solid-state NMR spectra due to the Fig. 1 shows the most common structures of Hilliard17,18,21 and
averaging out of anisotropic interactions, most importantly the Ahn21–23 adducts synthesized and characterized so far. Importantly,
Chemical Shift Anisotropy (CSA).8,9 Finally, it should be noted all adducts are safe and robust with respect to mechanical and
that phosphine oxides are important synthetic targets and thermal impact. Even when bringing the powders directly into a
intermediates.10,11 For example, they are byproducts of the flame, the oxygen escapes without a pronounced audible or
Mitsunobu reaction,11g and recently became the focus of atten-
tion as redox-free Mitsunobu organocatalysts.11h
One of the most important features of phosphine oxides is
that they form hydrogen bonds with a variety of different donors.
For example, phenols have been used in combination with
Department of Chemistry, Texas A&M University, College Station, TX, 77842-3012,
USA. E-mail: bluemel@tamu.edu
Fig. 1 Selected previously reported Hilliard adducts (R = Cy, tBu, Ph,
† Electronic supplementary information (ESI) available: Crystallography data avail-
o-Tol, p-Tol)17,18,21 and Ahn adducts (R, = Cy, Ph, Et; R0, R00 = Me, Et, Pr,
able. CCDC 1945941 (1), 1449057 (2), 1449061 (3) and 1452863 (4). For ESI and
(CH2)5–7).21–23
crystallographic data in CIF or other electronic format see DOI: 10.1039/c9nj04858h
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visual effect. These stable, solid Hilliard and Ahn adducts are
easy to synthesize, they crystallize readily, and are currently
investigated regarding their potential as oxidizers.21–23
Peroxides are ubiquitous and immensely important in daily
life, medicine, academia, and industry.24–27 Recent applications in
synthesis include the oxidation of amines28 and sulfides,29 alkane
activation,30 epoxidations,31 and Baeyer–Villiger oxidations.23,32
Unfortunately, the most ubiquitous oxidizing agent, aqueous
H2O2, is far from ideal. The abundance of water it inevitably
delivers to the reaction mixture can lead to unwanted secondary
reactions. Additionally, most oxidations have to be performed in
a biphasic system, slowing rates and requiring phase separa-
tions later. Commercial aqueous H2O2 also contains nitric acid
as stabilizer. Aqueous H2O2 degrades at unpredictable rates,33
especially in the presence of metal ion traces33c and requires
titration prior to critical applications.33a,b Water-free formulations of
H2O2, like urea hydrogen peroxide (UHP)34 and peroxocarbonates35
do not have well-defined compositions and are insoluble in organic
solvents. Encapsulated versions of H2O2,36 and its adducts of metal
complexes are known but not readily available commercially or
synthetically.37,38 The peroxides (Me3SiO)2 and (CH3)2C(OO)
(DMDO) are applied, but their synthesis and storage are
problematic.38,39
Fig. 2 The new materials 1 and 2.
In this contribution we describe the creation of a solid,
crystalline network with well-defined composition that stabilizes
H2O2 by hydrogen-bonding to the PQO groups of dcpe dioxide
(bis(dicyclohexylphosphino)ethane dioxide). Furthermore, we
report a selective synthesis and the stabilization of a MEKPO
(methyl ethyl ketone peroxide) dimer by hydrogen-bonding with
dppe dioxide. Again, an extended network is obtained that has
also been characterized by single crystal X-ray diffraction.
Reaction of acetylacetone with aqueous H2O2, in the presence
or absence of a phosphine oxide resulted in the formation of
two cyclic peroxides.
Fig. 3 Single crystal X-ray structure of the hydrogen peroxide adduct
[(CH2Cy2PO)2ꢀH2O2]n (1).41
opposite directions, with a dihedral angle of 1801. This structural
feature has been observed previously for Ahn adducts of dppe
(bis(diphenylphosphino)ethane) dioxide.22 Every H2O2 molecule
Results and discussion
Hilliard adducts17,18,21 (Fig. 1) have already proven to be safe, forms hydrogen bonds to two PQO groups of neighboring dcpe
soluble, and solid incarnations of H2O2 with known and dioxide molecules. The short distance of 1.755 Å between the
reproducible composition.
PQO oxygen and the H atoms corroborates the hydrogen
However, to render them more competitive with aqueous bonding, as this distance is even slightly shorter than the values
H2O2, the weight of the carrier phosphine oxide needs to be in the characteristic range that spans from 1.85 to 1.95 Å.42
reduced. One approach towards this goal is to offer a diphosphine Additionally, the hydrogen bonding manifests itself in the short
dioxide, bis(dicyclophosphino)ethane dioxide, for stabilizing the distance between the two O–Hꢀ ꢀ ꢀO oxygen atoms (2.704 Å),
H2O2. The envisioned species included a monomeric adduct which also lies slightly below the typical range of values from
with two intramolecular PQO groups, (CH2Cy2POꢀH2O2)2, and a 2.75 to 2.85 Å.43 The PQO groups are weakened and elongated
cyclic dimer containing four H2O2 molecules bridging four (1.501 Å) due to the hydrogen bonding, consistent with comparable
PQO functions, [(CH2Cy2POꢀH2O2)2]2. The formation of cyclic values of the Hilliard adducts described earlier.17,18,21
structures seemed likely, especially with respect to Shenderovich’s
work on cyclic trimers of phosphinic acids.40
The 31P NMR resonance of adduct 1 also has a different
chemical shift (53.78 ppm) than the signal of dcpe dioxide
However, when dcpe dioxide was reacted with aqueous (54.27 ppm). The hydrogen bonding does, however, not manifest
H2O2, an extended network with a zig-zag chain structure was in a different IR wavenumber for n(PQO) in 1, as the same value
formed (1, Fig. 2). The material 1 crystallized easily and could be of 1134 cmꢁ1 is measured for the neat compound dcpe dioxide.
investigated by single crystal X-ray diffraction (Fig. 3). The PQO The smaller differences in the IR and NMR chemical shift values,
groups of each diphosphine dioxide molecule are oriented in as compared to previously described Hilliard adducts17,18,21 are
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most probably due to the fact that in 1 only one hydrogen bond into a flame only leads to slow release of gas without pronounced
is formed between H2O2 and a PQO group, while the majority of visible or audible effects. Nevertheless, the active oxygen content
the Hilliard adducts have two. However, regarding the longterm of 2 amounts to 7.5 wt%, which is close to the range of
stability of material 1, it compares favorably with dimeric commercially available MEKPO for academic use (32–35 wt%
Hilliard adducts. For example, after about three years of storage solutions with 8.7–9.0 wt% active oxygen).
in the laboratory atmosphere at room temperature (22 1C), solid
In order to determine the longevity of peroxides that are
1 retained 58% of its original oxidative power. Under the same stabilized by hydrogen-bonding in Hilliard17,18,21 or Ahn
conditions, after ca. three years, ( p-Tol3POꢀH2O2)2 only retains adducts,21–23 we have previously developed a method to quickly
33% of its oxidative power.18
determine their oxidative power. The method is based on
Based on the experience that phosphine oxides can efficiently offering the peroxide a weighed amount of PPh3 in excess
stabilize bis(dihydroperoxy)alkanes via hydrogen bonding to form and integrating the 31P NMR signals of residual PPh3 and
Ahn adducts,21–23 we sought to create an Ahn adduct with reduced produced OPPh3 after the oxidation reaction.21 Accordingly,
weight of the phosphine oxide carrier. This should render Ahn for material 2, an oxidative power of 100% would correspond to
adducts more competitive with respect to the commercially available three active oxygen atoms per adduct unit (Fig. 2). It turns out
aqueous H2O2. We approached the new synthesis by using the that the peroxide in 2 is stabilized very well by the dppe dioxide,
dioxide of bis(diphenylphosphino)ethane (dppe dioxide) as carrier and after 4.7 years of exposure to the atmosphere in a drawer in
with lower weight and sought to produce the Ahn adduct the lab at ambient temperature its remaining oxidative power
(CH2Ph2POꢀ(HOO)2CMeEt)2, in analogy to (CH2Ph2POꢀ(HOO)2CEt2)2 still amounts to 24%.
that has been reported previously.22
Material 2 crystallizes readily and in large habits, and there-
Interestingly, when butanone was reacted with aqueous fore the structure could also be characterized by single crystal
H2O2 in the presence of dppe dioxide, the dimeric peroxide X-ray diffraction (Fig. 4).
(HOOCMeEtO)2 was obtained. This peroxide dimer is stabilized
The two ketal carbon atoms in the dimeric peroxide component
by forming a hydrogen-bonded extended network with dppe of the network display R and S configurations, therewith con-
dioxide, [(CH2Ph2PO)2ꢀ(HOOCMeEtO)2]n (2) (Fig. 2). The material stituting the meso compound. The two hydroperoxy groups are
2 is obtained in an unoptimized yield of 83%.
hydrogen-bonded to the phosphine oxide groups. The two
The selective formation of adduct 2 is remarkable regarding hydrogen-bonded PQO groups of the dppe dioxide point in
the properties and especially the reactivity of MEKPO (methyl opposite directions with a dihedral angle of 1801, in analogy to
ethyl ketone peroxides). MEKPO represents an indispensable the extended network of material 1. The ideal packing with dppe
class of reagents in the polymer industry, where it is used as a dioxide (Fig. 4) may promote the formation of the dimeric
catalyst for acrylic resins or as curing agent for unsaturated peroxide as opposed to the di(hydroperoxy)butane moieties
polyester resins.44,45 However, despite its importance, it is found in the adducts Ph3POꢀ(HOO)2CEtMe and Cy3POꢀ(HOO)2-
regarded as a very hazardous material. Therefore, great efforts CEtMe.22 The crucial factor explaining the ease of crystallization
have been undertaken to produce MEKPO under controlled of material 2 and favoring the structure of the network might be
reaction conditions and on small scales, for example, by using a the similar lengths of the P–C–C–P (4.412 Å) unit of the dipho-
microreactor.45 At present, MEKPO oligomers are synthesized sphine dioxide and the C–O–O–C (3.571 Å) moiety of the dimeric
by reacting butanone (MEK, methyl ethyl ketone) with H2O2 in peroxide, which allow for their parallel and strainless stacking in the
a batchwise manner. The initial product is most probably crystal. The slight difference in the lengths allows the hydrogen
EtC(OH)(OOH)Me that undergoes secondary reactions to yield bonds to retain the favorable linear OꢀꢀꢀH–O arrangement.
a mixture of linear and cyclic oligomers.44 These oligomers are
Every MEKPO moiety forms hydrogen bonds to two PQO
impossible to separate economically and therefore MEKPO is groups of adjacent dppe dioxide molecules. The distance of
applied as a mixture based on the wt% of active oxygen.44,45 1.783 Å between the PQO oxygen and the H atoms indicates the
Industrial batches of MEKPO still contain residual MEK which
increases its explosion hazard. Additionally, for industrial appli-
cations MEKPO is diluted with DMP (o-dimethylphthalate) to
40–60% solutions. Furthermore, it is a strong oxidizing agent
and a corrosive. Acute and chronic toxicity can occur as an
occupational hazard. Inhalation of MEKPO can lead to pneumonitis,
acidosis, and liver and renal failure.46 Finally, MEKPO is prone to
runaway reactions when coming into contact with a variety of
substances, for example, bases, or Fe(II/III) salts.47
In contrast, material 2 is a much more benign version of
MEKPO. It is solid, has a low vapor pressure, and besides the
phosphine oxide carrier it is free of additives. Material 2 exhibits
a well-defined composition and is less prone to uncontrolled
decomposition. In fact, when mechanical stress like grinding or
hammering are applied, no detonation occurs and bringing 2
Fig. 4 Single crystal X-ray structure of adduct 2.41
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hydrogen bonding, being even slightly shorter than the values
in the characteristic range from 1.85 to 1.95 Å.42 Furthermore,
the hydrogen bonding leads to a short distance between the two
O–Hꢀ ꢀ ꢀO oxygen atoms (2.627 Å), which is slightly outside at the
lower end of the typical range of values (2.75 to 2.85 Å).43 The
PQO groups are elongated (1.497 Å) due to the hydrogen
bonding, consistent with comparable values of the Ahn adducts
described earlier.21–23 Correspondingly, the 31P NMR resonance
of 2 undergoes a downfield shift to 36.91 ppm with respect to
31.5 ppm reported for the adduct-free dppe dioxide.48 The
hydrogen bonding also manifests in the slight lowering of the
IR wavenumber n(PQO) in 2 to 1173 cmꢁ1 as compared to
1175 cmꢁ1 for dppe dioxide.48
Scheme 1 Synthesis of the cyclic dioxolane derivative 3.
H2O2 to form selectively the trans-cycloperoxides 3 (Scheme 1).
The presence of nitric acid as stabilizer in the aqueous H2O2
most probably facilitates the nucleophilic attacks. However, it is
remarkable that no I2 was needed as a catalyst to create the
dioxolane as reported for similar 1,3-diketone transformations to
dioxolanes previously.53 In contrast to earlier reports of cis/trans
mixtures,52 only the trans isomer of 3 was obtained. Further-
more, in the sole presence of H2O2 and strong acids, bridged
tetraoxanes have been reported.51
Depending on the amount of H2O2, either trans-3,5-dimethyl-
1,2-dioxolane-3,5-diol (3) or trans-3,5-dihydroperoxy-3,5-dimethyl-
1,2-dioxolane (4) is isolated as the sole product (Fig. 5). Curiously,
the mixed dioxolane 5,52 containing one OH and one OOH
substituent (Fig. 5), was not observed.
It is remarkable that only the trans isomers are formed in
both cases, while in the literature cis/trans isomer mixtures of 3
and 4 are obtained by different syntheses.52,54
Since both 3 and 4 crystallize readily, the trans substitution
is also proven by their single crystal X-ray structures.41,55 Fig. 6
displays the structure of 3,41 the structure of 4 is in accord with
the literature.41,54,55
Similarly to the Ahn adducts described previously,21–23 the
solubility of 2 is highest in methylene chloride (66.9 mg mLꢁ1).
It is relatively low in benzene (1.43 mg mLꢁ1), methanol
(1.72 mg mLꢁ1), and dimethylformamide (2.24 mg mLꢁ1). Most
probably, the nature of 2 with its extended hydrogen-bonded
network leads to the comparatively low solubilities in the latter
three solvents. Dichloromethane, due to its ability to strongly
interact with PQO groups,19 might be able to split 2 into
smaller, more soluble fragments of the network. It has been
demonstrated earlier by DOSY experiments that in methylene
chloride dimeric Hilliard adducts with triarylphosphine oxide
carriers are dissociating into monomers.18 Nevertheless, it is
noteworthy that even the lower solubilities are more than
sufficient for potential applications of 2 as a polymerization
starter.49
Since dppe dioxide proved to be able to form multiple
hydrogen bonds to di(hydroperoxy)alkanes, the next step in
our synthesis endeavor involved expanding the scope of offered
ketones to diketones. In this way, the weight of the adduct
assemblies per active oxygen atom could be reduced. Further-
Both dioxolanes 3 and 4 form an intricate network of
hydrogen bonds with neighboring molecules (Fig. 6), which
may be the reason for their ease of crystallization. Furthermore,
these intermolecular hydrogen bonds might compete with the
adduct formation via the PQO groups of the phosphine oxides,
in this way favoring the cyclic molecular products 3 and 4.
more, we sought to probe whether both carbonyl groups of a
21,22
diketone could undergo nucleophilic attack by H2O2
to
each form the di(hydroperoxy)alkane moiety. The latter would
be stabilized immediately by hydrogen-bonding to the offered
phosphine oxide groups.
To test this idea, acetylacetone was selected as the 1,3-diketone
because it is very versatile and, depending on the reaction
conditions and additives, it can yield a variety of different
products.50–52 Dppp dioxide (bis(diphenylphosphino)propane
dioxide) was chosen as the phosphine oxide partner. The
PQO groups are in close enough proximity to form strong hydrogen
bonds, while the (CH2)3 tether between them should allow for
sufficient flexibility to orient them towards the two di(hydro-
peroxy)alkane moieties potentially created from acetylacetone.
Interestingly, the presence of dppp dioxide does not prevent
the cyclization of the diketone when being treated with aqueous
H2O2. This result is in contrast to the cases of previously
reported adducts, where the phosphine oxides formed hydro-
gen bonds with the di(hydroperoxy)alkane moieties and thereby
prevented the condensation leading to cyclic acetone peroxide
or butanone peroxide.21–23 The cyclic peroxide 3 is formed
according to the pathway displayed in Scheme 1. Acetylacetone
undergoes two consecutive nucleophilic attacks by aqueous
Fig. 5 Possible products of the reaction of acetylacetone with aqueous
H2O2. Only 3 and 4, but not 5 were observed experimentally.
Fig. 6 Single crystal X-ray structure of 3 (left) and 3 in the unit cell
(right).41
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It is also noteworthy that compounds 3 and 4 could be was obtained from Acros Organics and used as received. Solvents
obtained selectively and isolated in high yields of 71% and 68%, were dried by boiling them over sodium, then they were distilled
respectively. No elaborate purification operations like column and stored under purified nitrogen. Dichloromethane (Aldrich,
chromatography, and no catalysts like I2 and SnCl2ꢀ2H2O were ACS reagent grade) was dried over 3 Å molecular sieves (EMD
needed.52,54 Furthermore, the aqueous H2O2 used was not as Chemical Inc.) prior to use.
concentrated with 35 wt% (compared to 50 wt%) and no
NMR Spectroscopy
concentrated H2SO4 had to be added, in contrast to a previously
described procedure.54
The 1H, 13C, and 31P NMR spectra were recorded at 499.70,
125.66, and 202.28 MHz on a 500 MHz Varian spectrometer.
The 13C and 31P NMR spectra were recorded with 1H decoupling.
Neat Ph2PCl (d(31P) = +81.92 ppm) in a capillary centered in the
5 mm NMR tubes was used for referencing the 31P chemical
shifts. For referencing the 1H and 13C chemical shifts the residual
proton and the carbon signals of the solvents were used (C6D6:
d(1H) = 7.16 ppm, d(13C) = 128.00 ppm; CDCl3: d(1H) = 7.26 ppm,
d(13C) = 77.00 ppm). The signal assignments are based on
1H,1H-COSY, 1H,13C-HSQC, and 1H,13C-HMBC NMR spectra.
Virtual couplings are indicated and the frequency distances of
the outer lines are reported.56
Conclusion
For preparative chemistry, the ideal peroxide would be inexpensive,
easily accessible, reproducible in its composition, and soluble in
organic solvents. It should be safe and stable at ambient
temperatures on the shelf. Finally, a solid oxidizing agent would
be desirable that can easily be administered.
In this contribution we describe the easy synthesis, purification,
and characterization of a H2O2 adduct of a diphosphine dioxide
(1), and an adduct containing a MEKPO dimer (2). Furthermore,
the selective syntheses of two dioxolane derivatives (3 and 4) are
described.
Synthesis and characterization
Bis(dicyclohexylphosphino)ethane dioxide H2O2 adduct
The reaction of bis(dicyclohexylphosphino)ethane dioxide
with hydrogen peroxide leads to an extended crystalline net-
work based on the formation of hydrogen bonds with the PQO
groups of the diphosphine dioxide. The novel structural motif
of the network is characterized by X-ray diffraction. Further-
more, a new selective synthesis for an industrially important
MEKPO dimer and its stabilization by a diphosphine dioxide is
described. The dimer is created by reaction of dppe dioxide
with butanone and aqueous hydrogen peroxide. This dimeric
peroxide is stabilized by strong hydrogen bonds to the phosphine
oxide groups within an extended network, which has been
characterized by single crystal X-ray diffraction. The dimeric
peroxide material can easily be purified by crystallization. It is
solid with a low vapor pressure and therefore poses less of a
health hazard at the workplace than pure MEKPO. Phosphine
oxide-supported MEKPO does not show tendencies to explode
and is stable on the shelf at ambient temperatures over years.
Furthermore, it is soluble in organic solvents, with the highest
solubility in methylene chloride. In summary, material 2 might
be an attractive alternative to MEKPO in the future.
[Cy2POCH2CH2POCy2ꢀH2O2]n (1).
Bis(dicyclohexylphosphino)ethane (169 mg, 0.4 mmol) is placed
in a Schlenk flask under nitrogen atmosphere and dissolved in
dichloromethane (1.4 mL). While stirring vigorously, aqueous
hydrogen peroxide is added (0.6 mL, 35%, 7 mmol) and the
biphasic mixture is stirred for 30 min. The phases are separated,
and the organic phase is layered with 5 mL of pentane. After
slow evaporation of the solvents, adduct 1 is obtained in the
form of colorless needles (149 mg, 0.30 mmol, 76%). Melting
range (decomp.) 135–145 1C.
NMR (d, CDCl3), 31P{1H} 53.78 (s); H 7.65 (br. s, 2H, OOH),
1
2
1.93 (s, 4H, H5), 1.91 (d, J(1H–1H) = 16.4 Hz, 8H, H2eq), 1.85–
1.72 (m, 12H, H1, H3eq), 1.71–1.63 (m, 4H, H4eq), 1.34 (q,
3J(1H–1H) = 10.4 Hz, 8H, H2ax), 1.27–1.14 (m, 2H, H3ax, H4ax);
13C{1H} 36.26 (virtual triplet, 93.4 Hz, C1), 26.53 (virtual triplet,
12.1 Hz, C3), 25.87 (s, C4), 25.57 (virtual triplet, 28.8 Hz, C2),
The reaction of acetylacetone with aqueous H2O2, irrespective
of the presence of phosphine oxide, leads to the unprecedented
stereoselective formation of two dioxolane derivatives in high
isolated yields. Both cyclic peroxides have been obtained in
crystalline forms suitable for single crystal X-ray diffractions and
their stereochemistry has been determined.
15.10 (virtual triplet, 92.9 Hz, C5). IR: n(O–H) = 3159 cmꢁ1
n(PQO) = 1134 cmꢁ1
,
.
Bis(diphenylphosphino)ethane dioxide (2,20-peroxydi(butane-
2-peroxol)) adduct [(CH2Ph2P(O))2ꢀ(HOOCMeEtO)2]n (2). Bis(di-
phenylphosphino)ethane (dppe) dioxide (103 mg, 0.24 mmol) is
dissolved in toluene (10 mL) in a round bottom flask. Butanone
(10 mL, 112 mmol) and aqueous H2O2 (0.1 mL, 35%, 1.2 mmol) is
added, and the reaction mixture is stirred overnight. The solution
is concentrated to 5 mL in vacuum, then the mixture is left to
Experimental
General considerations
All reactions were carried out using standard Schlenk line stand exposed to the atmosphere, so that the product can
techniques and a purified N2 atmosphere, if not stated otherwise. crystallize. Adduct 2 is obtained in the form of large, colorless,
Reagents purchased from Sigma Aldrich or VWR were used rectangular crystals (126 mg, 0.20 mmol, 83% yield). M.p.
without further purification. Aqueous H2O2 solution (35% w/w) (decomp.) 4176 1C.
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Hm), 2.59 (d, 2J(31P–1H) = 2.7 Hz, 4H, PCH2), 1.81 (q, 3J(1H–1H) =
7.6 Hz, 4H, CH2CH3), 1.44 (s, 6H, CCH3), 1.03 (t, 3J(1H–1H) =
7.6 Hz, 6H, CH2CH3); 13C{1H} 132.49 (s, Cp), 130.73 (virtual triplet,
102.8 Hz, Ci), 130.70 (virtual triplet, 9.4 Hz, Co), 129.08 (virtual
triplet, 12.2 Hz, Cm), 111.73 (s, CCH3), 26.15 (s, CH2CH3), 21.31
(virtual triplet, 66.0 Hz, PCH2), 17.49 (s, CCH3), 8.39 (s, CH2CH3).
IR: n(O–H) = 3254 cmꢁ1, n(PQO) = 1173 cmꢁ1
.
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trans-3,5-Dimethyl-3,5-diol-1,2-dioxolane (3). Dppp (bis(diphenyl-
phosphino)propane) (1.001 g, 2.43 mmol) is dissolved in dichloro-
methane (60 mL). Aqueous H2O2 (5.0 mL, 35%, 58 mmol) is added,
and the solution is stirred for 1 h. The organic layer is collected
using a separation funnel, and the solvent is removed in vacuo.
The resulting white residue is dissolved in acetylacetone
(2.5 mL, 24.3 mmol), followed by the addition of excess aqueous
H2O2 (0.1 mL, 35%, 1.2 mmol). The solution is stirred for 3 d,
then the mixture is allowed to stand for crystallization. The
product 3 is obtained in the form of white, crystalline needles
(94 mg, 0.71 mmol, 71% yield with respect to amount of H2O2
added to the acetylacetone).
Alternative procedure. Acetylacetone (100 mg, 1 mmol) is
weighed into a vial and aqueous H2O2 (0.15 mL, 35%, 1.7 mmol)
is added. The solution is stirred overnight, and most of the water
is removed in vacuo. Benzene (1.0 mL) is added to precipitate the
product, which is filtered and dried in vacuo (83 mg, 0.62 mmol,
62% yield). M.p. (decomp.) 82 1C.
1
NMR (d, CDCl3), H 2.74 (s, 2H, CH2), 1.63 (s, 6H, CH3); 13C
1
105.50 (s, OC), 55.23 (CH2), 22.59 (CH3). H and 13C NMR data
match literature values.52
trans-3,5-Dihydroperoxy-3,5-dimethyl-1,2-dioxolane (4). Acetyl-
acetone (100 mg, 1 mmol) is weighed into a vial and combined
with 1.0 mL (10 mmol) of aqueous H2O2. The solution is stirred
overnight, and the excess of water is removed in vacuo. The
product precipitates when benzene (1.0 mL) is added (113 mg,
0.68 mmol, 68% yield). M.p. (decomp.) 98 1C.
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1
(s, 6H, CH3); 13C 112.99 (s, OC), 51.11 (CH2), 17.52 (CH3). H
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Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
This work was supported by the National Science Foundation
(CHE-1300208 and CHE-1900100).
Notes and references
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with the same crystal system (monoclinic) and space group
(P21/n) (CCDC 1487205†, Refcode YAFDER), synthesized by using
50 wt% H2O2 and concentrated H2SO4, I2, and SnCl2ꢀ2H2O as
catalysts, and crystallized from a dichloromethane/ethyl acetate
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follows (cited values) a = 5.5661(6) Å (5.5729(5) Å), b =
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b
= 92.306(3)1 (90.055(4)1), volume =
759.20(13) Å3
(751.17(11) Å3), R1 [I 4 2s(I)] = 5.07% (6.18%), R1 (all data) =
6.76% (8.03%).
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This journal is ©The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
New J. Chem., 2019, 43, 17174--17181 | 17181