Complete Double Epoxidation of Divinylbenzene Using Mn(porphyrin)-Based Porous Organic Polymers

Article abstract of DOI:10.1021/acscatal.5b01388

A series of porphyrin-based porous organic polymers (PPOPs) were synthesized in excellent yields via the Yamamoto-Ullmann couplings of tetrabromo spirobifluorene with several brominated porphyrin monomers. After isolation and demetalation, the metal-free PPOP can be postsynthetically metalated to form a Mn^III-PPOP that is catalytically active toward the selective double-epoxidation of divinylbenzene to divinylbenzene dioxide. (Chemical Equation Presented).

Full text of DOI:10.1021/acscatal.5b01388

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The complete double epoxidation of divinylbenzene
using Mn(porphyrin)ꢀbased porous organic polymers
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Kainan Zhang, Omar K. Farha,* Joseph T. Hupp,* SonBinh T. Nguyen*
Department of Chemistry and International Institute for Nanotechnology, Northwestern
University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, USA
ABSTRACT. A series of porphyrinꢀbased porous organic polymers (PPOPs) were synthesized
in excellent yields via the YamamotoꢀUllmann couplings of tetrabromo spirobifluorene with
several brominated porphyrin monomers. After isolation and demetallation, the metalꢀfree PPOP
can be postꢀsynthetically metallated to form a MnIIIꢀPPOP that is catalytically active towards the
selective doubleꢀepoxidation of divinylbenzene (DVB) to divinylbenzene dioxide (DVBDO).
KEYWORDS.
Mn(porphyrin), porous organic polymer, epoxidation, divinylbenzene,
divinylbenzene dioxide.
The synthesis of multiepoxides from available multiolefin precursors is a key process in the
preparation of epoxy resins, a class of technologically important materials with excellent
mechanical and electrical insulating properties as well as good resistances to chemicals and
temperature.1 Among the multiepoxides that are currently in use, divinyl benzene dioxide
(DVBDO) is an important popular and highꢀtech component in epoxy thermoset formulations for
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use as coatings, structural components, and modeling composites.2 Yet to date, there are only a
handful of catalytic processes reported for the preparation of DVBDO3ꢀ5 often with low
conversion and broad product mixtures.2,4ꢀ6 Thus, a catalyst that can epoxidize divinyl benzene
(DVB) to DVBDO with good conversion and selectivity is highly desirable. Herein, we report a
porous organic polymer (POP) catalyst that can successfully accomplish this goal through a
microporous environment with multiple catalyst entities that can encapsulate DVB and oxidize
both of its olefin groups.
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Although metalloporphyrins have been intensively studied as epoxidation catalysts given their
high activities and close biological relevance to natural enzymes,7ꢀ13 their utilities in
homogeneous epoxidation have been rather limited due to several deactivation pathways such as
dimerization13 and selfꢀoxidation.14 To achieve more stabilized and active catalytic systems,
metalloporphyrins have been anchored to solid supports15 as well as being integrated into porous
materials such as metal organic framworks (MOFs) 16ꢀ20 and porous organic polymers (POPs).21ꢀ
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In particular, the integration of metalloporphyrins into porous frameworks have been found to
lead to unexpected benefits, such as shapeꢀ and sizeꢀselectivity,26,32 and increases in reaction rate
due to preconcentration effects.29 It is this latter effect that prompted us to examine the double
epoxidation of DVB inside a microporous metalloporphyrinꢀbased POP. We hypothesize that a
preꢀconcentration of DVB inside the pores of an appropriately designed metalloporphyrinꢀbased
POP would lead to its complete double epoxidation due to the ability of adjacent catalyst
moieties to interact with both vinyl functionalities. As shown below, this is indeed the case:
excellent catalytic reactivity and high selectivity can be achieved for the double epoxidation of
DVB to DVBDO using a microporous POP derived from spirobifluorene and porphyrinꢀbased
building blocks.
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While metalloporphyrins have previously been incorporated into POPs22,31 and used for sulfide
oxidation, alkene expoxidation,31 as well as hydrogen peroxide decomposition,33 these early
materials have relatively moderate surface areas, which limit the range of substrates and oxidants
that can be used. To overcome these limitations, we selected the spirobifluorene monomer A as
the structureꢀdirecting comonomer in our synthesis of porphyrinꢀbased POPs (PPOPs) using
YamamotoꢀUllmann couplings34ꢀ38 given its tendency to afford POP materials with excellent
thermoꢀstability, high microporosity as well as moderate mesoporosity (based on the pore size
distribution data, there are micropores at about 7 Å and 12 Å and broad hump in the mesoporous
region ranging from 20 ~ 40 Å).34ꢀ37 For the porphyrin components, we examined both the
dibromide derivatives 1 and the tetrabromide derivatives 2 (Figure 1). Curiously, while the
couplings between A and either the freeꢀbase porphyrins (1 and 2) or the Fe(porphyrin)
monomers (Fe1 and Fe2) under various stoichiometric ratios proceed in good yields (see
Supporting Information (SI)), the analogous couplings with the Mn(porphyrin) monomers failed.
Presumably, the Ni(COD)2 reagent may have been oxidized by the MnIII center, leading to
deactivation.
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Figure 1. Monomers for YamamotoꢀUllmann coupling.
As common in YamamotoꢀUllmann couplings, strong acidic workꢀup is required to remove all
the Ni side products. Upon this acidic workꢀup, the Feꢀcontaining PPOPs AnFe1 and AnFe2
(subscript n = 1ꢀ3, indicating the relative stoichiometry of A vs those for Fe1 and Fe2), readily
demetallate to form partially metallated, or fully demetallated PPOPs (Scheme 1, Table 1).
Complete demetallation can be achieved by a second acid treatment at 85 °C, giving rise to the
corresponding freeꢀbase PPOPs fbAnFe1 and fbAnFe2. In general, increasing the ratio of
spirobifluorene A to the porphyrin monomers lead to increases in specific surface areas (ssa’s)
(Table 1, cf. entries 1ꢀ3 and entries 4ꢀ6) of the resulting freeꢀbase PPOPs. Presumably, this can
be attributed to a higher degree of crossꢀlinking possible in Aꢀrich formulations.
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Br
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Br
Br
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Ni(COD)2
COD
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bipy
Br
+
DMF, 85 C, 15 h
n
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Br
Br
Br
HCl, 85 C
N
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DMF, 120 C,
2 days
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Cl
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overnight
n
n
Scheme 1. A schematic illustration of PPOP synthesis and subsequent demtallation and
metallation.
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Table 1. Characterization data for freeꢀbase PPOPs and MnꢀPPOPs.
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Surface area Total pore volume Metal loading
Entries
PPOPs
(m2/g)
760
(cm3/g)
0.35
0.26
0.46
0.23
0.57
0.64
0.94
(wt %)
< 0.1
0.16
fbAFe1
fbA2Fe1
fbA3Fe1
fbAFe2
fbA2Fe2
fbA3Fe2
fbA22
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< 0.1a
< 0.1
0.35b
Mn-fbA2Fe2
Mn-fbA22
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850
0.36
4.0
2.7
1600
0.79
aAs synthesized without further demetallation. Ni content
b
Interestingly, A22, the PPOP derived from the freeꢀbase porphyrin monomer 2 still retains a
significant amount of Ni after work up (see Table S1, entry 6 in the SI), presumably due to in
situ metallation by the NiBr2 side products. Nevertheless, most of this Ni contaminants can be
removed upon a second, more rigorous acid treatment at higher temperatures (85 °C and 10 h)
yielding a free base PPOP (fbA22) with BET surface area (Table 1, entry 7) and total pore volume
fb
that are almost twice those of A2Fe2, the demetallated freeꢀbase PPOP derived from A2Fe2,
which has the same spirobifluorene:porphyrin stoichiometry (Table 1, cf. entries 5 and 7). As
expected for a material with aromatic C–C connections, PPOP fbA22 is highly stable: it retains a
high surface area (1540 m2/g) after being exposed to either concentrated hydrochloric acid or 4
M aqueous sodium hydroxide (see Figure S56 in the SI).
Metallation of both fbA22 and fbA2Fe2 with MnCl2·4H2O39ꢀ45 was carried out under previously
established conditions31 (Scheme 1). Interestingly, fbA2Fe2 can be metallated near quantitatively
fb
while A22 is only metallated to about 67%. Treating this metallated material with additional
MnCl2·4H2O under the same conditions does not lead to any further increase in metal loadings.
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Consistent with this observation, the diffuseꢀreflectance UVꢀvis spectrum of the Mn-fbA22
material (Figure S61 in the SI) also shows residual bands due to nonꢀmetallated materials.
Metallation only moderately decreases the surface areas for Mn-fbA22 and Mn-fbA2Fe2 from
the parent freeꢀbase PPOP (Figure 2; Table 1, cf. entries 3 vs 8 and 7 vs 9, respectively).
Notably, Mn-fbA22 retained most of the mesoporosity of the parent PPOP (Figure 3), which
would be benificial in applications such as catalysis where massꢀtransport limitation can be quite
important. However, the pore size distribution data for Mn-fbA2Fe2 shows almost complete
reduction of mesoporosity (Figure 3), a fact that is supported by a reduction of the hysteresis in
the N2 isotherms (Figure 2). Nevertheless, the dominant remaining micropore (~ 11 Å) for this
material is still large enough for DVB (~ 7 Å) and DVBDO (~ 9 Å) to access.
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Figure 2. Stacked N2 isotherm data for fbA22 (blue), Mn-fbA22 (red), A2Fe2 (green), and Mn-
fbA2Fe2 (purple).
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Pore Width (Å)
Figure 3. Stacked NLDFT (NonꢀLocal Density Functional Theory) pore size distribtions for
fbA22 (blue), Mn-fbA22 (red), fbA2Fe2 (green), and Mn-fbA2Fe2 (purple). These pore size
distributions are stacked by moving about 0.005 cm3 up and down for clarity. These single data
can be seen in SI with a unit on y axis as incremental pore volume.
Mn-fbA22 was then evaluated as catalyst for the epoxidation reaction of styrene and DVB in
the presence of 2ꢀ(tert-butylsulfonyl)iodosylbenzene (5) oxidant (Scheme 2).31,46,47 As shown in
Figure 4, the epoxidation of styrene affords good yield (80%) of styrene oxide with no
significant mass loss (see Figures S62 in the SI for the NMR spectra of the reaction mixture).
This is in stark contrast to the homogeneous (TPP)MnCl analogue (TTP = mesoꢀ
tetraphenylporphyrinato dianion), which affords lower yield of styrene oxide in addition to the
overꢀoxidized product benzaldehyde and the isomerization product phenyl acetylaldehyde. This
homogeneous catalyst also decomposed much more easily, as shown by the change in conversion
profile after ~15 h (Figure 4).
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Scheme 2. The epoxidation of styrene by Mn-fbA22 (top) and (TPP)MnCl (bottom).
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styrene heterogeneous
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styrene oxide homogeneous
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Figure 4. Comparison of styrene epoxidation using Mn-fbA22, and (TPP)MnCl.
Consistent with the aforementioned promising styrene oxidation results, both Mn-fbA22 and
Mn-fbA2Fe2 show comparable good yields and selectivities towards the complete expoxidation
of DVB to DVBDO, with > 50% yield based on DVB (Scheme 3; Figure 5 and Figure S74 in the
SI). Only a trace (10 mol %) of the incomplete oxidation product divinylbenzene monoxide
(DVBMO) was found and no epoxide ringꢀopening product was observed (Figure 5). A
moderate amount (~24 mol %) of overoxidation product (benzyladehyde derivative) exists at the
end of the reaction, which may arise from the oxidative cleavage of the phenylacetylaldehyde
derivative (Scheme 4).48ꢀ50
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Scheme 3. The epoxidation of DVB by Mn-fbA22.
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epoxide
phenylacetaldehyde
benzaldehyde
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Figure 5. Plots of normalized concentrations of alkene, epoxide, phenyl acetaldehydes, and
benzaldehydes as functions of time in the epoxidation DVB by Mn-fbA22. At the end of the
reaction, about 20% of the reaction mass was compounds that could not be identified and thus
was not accounted for in these plots. These compounds are attributed to potential side reactions
of DVB (see further discussion below). The corresponding plots for Mn-fbA2Fe2 can be found
in Figure S74 in the SI.
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Scheme 4. Proposed overoxidation pathway.
The advantages of the PPOP environment for DVB double epoxidation clearly stand out over
its homogenous analog (TPP)MnCl. Under the same reaction conditions (see SI for reaction
details), the homogeneous catalyst afforded much poor substrate conversion (Figure 6), with ~
30% alkene left in the reaction mixture after 30 hours. In addition, GCꢀMS analysis shows that
the major product is the partially epoxidized product DVBMO (DVBDO:DVBMO = 2:3). We
attribute the higher selectivity for DVBDO in reactions catalyzed by Mn-fbA22 to the high
concentrations of catalyst inside its pore: after DVB entered the pore of a PPOP particle and
became oxidized, the DVBMO product was still encapsulated inside the particle and had a good
chance to encounter a second metal oxo moieties prior to existing the POP particle. Such multiꢀ
catalyst environment obviously does not exist in reaction catalyzed by the homogeneous
(TPP)MnCl catalyst where DVBMO is the major product.
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epoxide (PPOP)
epoxide [(TPP)MnCl]
PPOP
alkene [(TPP)MnCl]
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Figure 6. Plots of normalized concentrations of alkene and epoxide in the epoxidation of DVB
by Mn-fbA22 and (TPP)MnCl.
When DVBMO is used as the substrate (Scheme 5), its epoxidation by Mn-fbA22 proceed in a
similar rate and conversion as the styrene epoxidation, indicating that the presence of the paraꢀ
epoxy functional group does not significantly affect the epoxidation of the remaining styrenic
C=C bond. However, there were almost no unidentified products: DVBDO was formed in 76%
yield, benzaldehyde derivatives were formed in 18% yield, and the phenylacetaldehyde products
constituted the remainder of the mass balance (Figure 7). As in the case for DVB oxidation, the
isomerized phenylacetaldehyde products formed rather quickly, maximized at ~8 h and then
decreased. The benzaldehyde product does not form until after phenylacetaldehyde has built up,
suggesting that most of the overꢀoxidation comes from isomerization. Together with the data
shown in Figure 5, these results indicate that the 20% of unidentified mass in the epoxidation of
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DVB can be attributed to its higher susceptibility to other side reaction such as alkene
polymerization in the presence of Mn centers with unpaired electrons.51ꢀ54
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Scheme 5. The epoxidation of DVBMO by Mn-fbA22
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DVBDO
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benzaldehyde
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Figure 7. Plots of normalized concentrations of alkene, epoxide, phenylacetaldehyde, and
benzaldehyde derivatives as functions of time in the epoxidation of DVBMO by Mn-fbA22.
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The conversion and selectivity of metalloporphyrinꢀcatalyzed epoxidation reaction can be
enhanced by the addition of additives such as imidazole or pyridine that can coordinate to the Mn
center.41,42,54,55 This is also the case for Mn-fbA22: in the presence of imidazole, the overall
epoxide yield is increased by an additional 19% (20% increase for overall DVBDO yield, see
Scheme 6). This increase in yield can be attributed to the ability of imidazole to significantly
inhibit the formation of isomerized and overoxidized byproducts (from 24% to 15% for
benzaldehyde) (see Figure S69 in the SI); the maxium phenylacetaldehyde yield during the
reaction is down from 20% to 6% at around 7 h (see Figure S69 in the SI). Presumably, the
coordination of imidazole to the Mn(porphyrin) significantly reduces its Lewis acidity and thus
isomerization and overoxidation (Figure 8).56,57
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Scheme 6. Epoxidation of DVB by Mn-fbA22 with imidazole.
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Figure 8. Normalized alkene concentration and epoxide yield for comparison of DVB
epoxidation with and without imidazole.
The timeꢀdependent selectivity profile for the epoxidation of DVB catalyzed by [Mn-fbA22 +
imidazole] (Figure 9) shows an early formation of DVBMO that begins to decrease after ~ 9
hour as DVBDO becomes dominate. However, the combined amounts of DVBMO and DVDBO
up to this point are much less than the amount of converted DVB, suggesting that both DVB and
the initially epoxidized DVBMO are preferentially trapped inside the pores. In this manner,
there is a good chance for DVB to encounter more than one catalytic site before being released
into the solution and be detected as either DVBMO or DVBDO. Indeed, DVBDO was not
observed until 4 h into the reaction. Together, these data further supports our aforementioned
hypothesis that the multicatalyst porous environment is quite crucial for the selective double
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epoxidation of DVB. Interestingly, the effect of imidazole in the presence of Mn-fbA2Fe2 is
much less than that for Mn-fbA22 (see Figure S75 in the SI). We attributed this to the less
likelihood of the smaller pores in the latter materials to accommodate the additional imidazole
ligands; that is, the smaller pores may destabilize the imidazole complex more.
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Figure 9. Plots of normalized DVB concentration, DVBDO yield (based on DVB), and
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It is important to note that recycling catalytic experiments are informative, however, we were
unable to recycle this catalyst since the oxidant byproduct tertꢀbutylsulfonyliodobenzene in the
reaction was well mixed with the catalyst; the latter is actually the major part. Even after
washing, we could not get clean catalysts and we lost most of it during the washing process due
to its fine powder form.
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In summary, we have demonstrated the synthesis of a highly robust porphyrinꢀbased POP
material with good surface areas that can be readily metallated with MnIII and then used for the
selective double epoxidation of DVB to DVBDO in the presence of 2ꢀ(tertꢀ
butylsulfonyl)iodosylbenzene. Together with reaction profiling, comparative studies against the
analogous homogeneous catalyst (TPP)MnCl suggest that the multicatalyst porous nature of the
Mn-fbA22 material is the primary factor responsible for this successful double epoxidation. Such
observations clearly set porous catalyst materials apart from other catalysts where the high
concentration of catalyst inside the pore plays a significant role in reaction outcome and
selectivity.
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ASSOCIATED CONTENT
Supporting Information. Procedure for synthesis of PPOPs, the material characterizations,
and procedures for conducting catalytic experiments. This material is available free of charge
via the Internet at t http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail:
oꢀfarha@northwestern.edu (O.K.F.); jꢀhupp@northwestern.edu (J.T.H.);
stn@northwestern.edu (S.T.N).
Author Contributions
K.Z., O.K.F., J.T.H., and S.T.N. conceived the experiments presented herein. K.Z. synthesized
all compounds, carried out the characterization of all polymers, and performed all the catalysis.
O.K.F., J.T.H., and S.T.N. supervised the project. K.Z. wrote the initial draft of the paper with
inputs and corrections from all coꢀauthors. K.Z. and S.T.N. finalized the manuscript.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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This work was supported by the Dow Chemical Company. NMR measurement is supported
by the National Science Foundation under CHEꢀ1048773. We thank Dr. Patricia Ignacio de
Leon.and Prof. Justin Notestein for helpful discussions.
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