Patent Grant
10766851
It is provided a method of converting a diaryl ether source such as lignin and/or polyphenylene oxide (PPO) into organic recycled compounds.
Converting lower value renewable biomass, e.g., forestry and agricultural wastes, and disused polymers such as polyphenylene oxide (PPO) into higher value-added chemical products is becoming increasingly important for social, economic, and resource sustainability. Lignin is a major renewable biomass waste product in the pulp and paper industry, with a production of 150-180 million tons per year. On the other hand, polyphenylene oxide (PPO) is widely used as important engineering-plastics. Diaryl ether, a common 4-O-5 linkage lignin model compound and the building block of PPO, has the highest bond dissociation energy among the three types of ether linkages (including α-O-4, β-O-4 and 4-O-5) in lignins, and is the most challenging to cleave. Thus far, success has been achieved to cleave this type of ether bond to form simple molecules, including hydrocarbon (benzene, cyclohexane) and oxygen-containing compounds (phenol, cyclohexanol, cyclohexanone, and cyclohexylalkyl ether).
Converting cheap inorganic chemicals into high value-added organic chemicals has very important economic value.
There is thus still a need to be provided with means to convert lower value renewable biomass into high value-added organic chemicals.
It is provided a method of converting a diaryl ether source containing 4-O-5 linkages and an inorganic chemical into organic compounds, comprising reacting said diaryl ether source with the inorganic chemical in presence of a catalyst, transforming the 4-O-5 linkages of said diaryl ether source into the organic compounds.
In an embodiment, the diaryl ether source is lignin, polyphenylene oxide (PPO), or a substituted diaryl ether.
In a further embodiment, the R1 and R2 are the same or different substituents on the arenes.
In another embodiment, the substituents are hydrogen, alkyl, halogen, alkoxyl, arylxy, ester, hydroxyl, amine, nitro, aryl or acyl groups.
In an additional embodiment, the inorganic chemical is urea, ammonium bicarbonate, ammonium chloride, hydrazine hydrate, ammonium hydroxide or ammonia gas.
In a particular embodiment, the catalyst is palladium.
In an embodiment, the catalyst is Pd(OH)2/C.
In another embodiment, the organic compound is at least one of an aniline derivative and an arene.
In a further embodiment, the method provided herein further comprises reacting said diaryl ether source, the inorganic chemical and the catalyst with a reducing agent.
In another embodiment, the reducing agent is HCO2Na, formic acid, ammonium formate, NaH, H2 or NaBH4.
In an embodiment, the method provided herein further comprises reacting said diaryl ether source, the inorganic chemical and the catalyst with a solvent.
In an embodiment, the solvent is m-xylene, o-xylene, p-xylene, toluene or 1,4-dioxane.
In a further embodiment, the diaryl ether source is reacted with 5 equiv of ammonium hydroxide.
In another embodiment, the reducing agent is 1 equiv of NaBH4.
In a further embodiment, the diaryl ether source, the inorganic chemical and the catalyst are contacted at a temperature between 140° C. to 160° C.
In an embodiment, the diaryl ether source and the inorganic chemical are contacted with 10 mol % to 30 mol % of the catalyst.
In a further embodiment, the said diaryl ether source, the inorganic chemical and the catalyst are reacted for 12 to 36 h.
Reference will now be made to the accompanying drawings.
It is provided a method of converting a diaryl ether source such as lignin and/or polyphenylene oxide (PPO) containing 4-O-5 linkages and an inorganic chemical such as ammonia into an organic compound, comprising reacting said diaryl ether source with the inorganic chemical in presence of a catalyst, preferably palladium, transforming the 4-O-5 linkages of said diaryl ether source into the organic compounds.
Accordingly, it is described a palladium-catalyzed synthesis of aniline derivatives from 4-O-5 linkage lignin model compounds and cheap industrial inorganic chemical ammonia via dual C(Ar)—O bond cleavage.
The conversion of renewable resources and cheap inorganic chemicals directly into higher value-added organic chemicals is becoming more and more important for future sustainable development. Lignin, being the second most abundant organic carbon renewable resource on Earth, has been treated as waste in the pulp and paper industry. The 4-O-5 linkage diaryl ether bond, is the strongest among the three types of ether linkages in lignins.
Ammonia is a very inexpensive industrial inorganic chemical. Herein, it is reported a direct conversion of diaryl ethers and ammonia into aniline derivatives and arenes, providing a model for selective lignin 4-O-5 linkage modification and PPO recycling with cheap ammonia. Both symmetrical and unsymmetrical diaryl ethers were successfully cross-coupled with ammonia via dual C(Ar)—O bond cleavages, generating the corresponding cyclohexylanilines and arenes.
Towards the valorization of lignin and PPO waste into higher value-added chemicals, it is provided a new method of reacting diaryl ethers with organic amines to form nitrogen-containing compounds.
Ammonia is a very cheap and abundant industrial inorganic chemical. Converting lignin or PPO waste with ammonia directly into high value-added nitrogen-containing organic chemicals provides a great economic advantage for lignin utilizations and PPO recycling. At the same time, anilines are important building blocks for various organic molecules and electronic materials, as well as among the most prevalent structural motifs among pharmaceutical agents. Thus, methods that can directly react lignin or PPO waste with ammonia to produce higher valued products were explored and herein, it is reported the direct transformation of 4-O-5 linkage lignin or PPO model diaryl ethers with ammonia into aniline derivatives, catalyzed by palladium (
Firstly, different palladium catalysts were screened to couple diphenyl ether with ammonium chloride (Table 1, entries 1-4).
aGeneral conditions: 1a (0.2 mmol), 2a (3 equiv), catalyst (20 mol %), HCO2Na (3 equiv), and solvent (1 mL) at 160 °C. for 24 h under an argon atmosphere.
bYields were determined by 1H NMR with nitromethane as internal standard, isolated yields in brackets.
cNH3 · H2O (2 equiv).
dNH3 · H2O (5 equiv).
eNH3 · H2O (6 equiv).
fNaBH4 (1.5 equiv).
gNaBH4 (1 equiv).
hNaBH4 (0.5 equiv).
i150° C.
j140° C.
kPd(OH)2/C (10 mol %).
lPd(OH)2/C (30 mol %).
m36 h.
n12 h.
Fortunately, a trace amount (ca 2% yield) of N-cyclohexylaniline was detected by 1H NMR when Pd(OH)2/C was used as a catalyst in toluene at 160° C. under an argon atmosphere for 24 h using sodium formate as a hydride source (Table 1, entry 1). Other palladium catalysts were also examined without success (Table 1, entries 2-4). Different solvents were then examined (Table 1, entries 5-6), and 6% yield of N-cyclohexylaniline was obtained when m-xylene was used as solvent (Table 1, entry 5). Encouraged by this result, different nitrogen sources such as urea, ammonium bicarbonate, ammonia, hydrazine hydrate and ammonia gas were investigated (Table 1, entries 7-11), with ammonia providing the highest yield (Table 1, entry 9). Adjusting the amount of ammonia to 5 equiv gave the optimal yield (Table 1, entry 13). Increasing or reducing the amount of ammonia led to lower yields (Table 1, entries 12 and 14). Using sodium borohydride, a strong reducing reagent, as hydride source, resulted in 49% yield of N-cyclohexylaniline together with 2% yield of diphenylamine (Table 1, entry 15). Using sodium hydride as the hydride source, a lower yield was observed (Table 1, entry 16). One equiv of NaBH4 appeared to be optimal for this reaction (Table 1, entry 18), as either higher or lower amounts of NaBH4 resulted in lower yields (Table 1, entries 17-19). Reducing the reaction temperature to 150° C. gave 87% yield of the product (Table 1, entry 20). Further reducing the temperature lowered the product yield (Table 1, entry 21). The amount of catalyst is also important for the reaction: a lower yield (64%) was achieved when 10 mol % catalyst was used in this reaction system (Table 1, entry 22), and further increasing the amount of catalyst to 30 mol % did not improve the yield (87%) (Table 1, entry 23). Thus, 20 mol % Pd(OH)2/C was selected as the optimal amount for subsequent optimizations. Nearly the same yield (88%) was obtained when prolonging the reaction time to 36 h (Table 1, entry 24). Reducing the reaction time to 12 h lowered the product yield (Table 1, entry 25). Different phosphine ligands (40 mol %) were tested, including triphenylphosphine, bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane and 1,4-bis(diphenylphosphino)butane, under the standard reaction conditions. These phosphine ligands could not improve the yield, and only recovered the starting material. It is thus provided that Pd(OH)2/C is reduced by NaBH4 to form Pd nanoparticles at 150° C. in the proposed catalytic system.
With the optimal reaction conditions established, different symmetrical diaryl ethers were explored to react with 5.0 equiv of ammonia at 150° C. under argon using 20 mol % of Pd(OH)2/C as the catalyst and 1.0 equiv of sodium borohydride in m-xylene (1 mL) for 24 h. As shown in Table 2, moderate to excellent yields were obtained for various substrates (Table 2, entries 1-7).
aReaction conditions: diaryl ether 1 (0.2 mmol), ammonia (1.0 mmol), Pd(OH)2/C (20 mol %), and NaBH4 (0.2 mmol) in m-xylene (1 mL). All reactions were carried out at 150° C. in a sealed tube under an argon atmosphere for 24 h; yields of isolated products were given.
bCis/trans (isomer) ratio was determined by crude 1H NMR.
cYields of benzene and cyclohexane was determined by GC-MS; a small peak of cyclohexane was overlapped within the big peak of benzene.
dYield was determined by GC-MS; no corresponding substituted cyclohexane was detected.
fReaction time was prolonged to 36 h.
Diphenyl ether was transformed into N-cyclohexylaniline in 83% yield, with the other phenyl group being converted into benzene (82%) as well as a small amount of cyclohexane (Table 2, entry 1). Weakly electron-donating methyl group at meta- and para-positions gave the corresponding anilines 3b and 3c in high yields (Table 2, entries 2-3). Similar results were obtained with longer chain analogs substituted at the para-position (Table 2, entries 4-5). The defluorination product 3a was obtained with moderate yield (48%) when fluorine-containing substrate 1f was explored under the standard conditions with prolonging the reaction time to 36 h and increasing the amount of NaBH4 to 2 equiv (Table 2, entry 6). The 4,4′-dimethoxyldiphenyl ether also reacted smoothly, to give the demethoxylation product 3a (Table 2, entry 7).
Subsequently, a wide range of unsymmetrical diaryl ethers were tested. Highly regioselective cleavage of C—O bond was obtained even with only a minute difference between the two aryl groups (Table 3, entries 1-2).
aReaction conditions: diaryl ether 1 (0.2 mmol), ammonia (1.0 mmol), Pd(OH)2/C (20 mol %), and NaBH4 (0.2 mmol) in m-xylene (1 mL). All reactions were carried out at 150° C. in a sealed tube under an argon atmosphere for 24 h; yields of isolated products were given.
bCis/trans (isomer) ratio was determined by crude 1H NMR,
cA trace amount of N-cyclohexylaniline and 8% of toluene were also obtained.
eIsolated yield.
fIsolated yield; 82% of cyclohexylbenzene was also obtained.
gIsolated yield; in addition, 74% of 1,2,3,4-tetrahydronaphthalene was obtained.
hIsolated yield; in addition, 76% of 1,2,3,4-tetrahydronaphthalene was obtained.
iIsolated yield; in addition, 81% of cyclohexylbenzene was obtained.
Thus, 3- and 4-methyldiphenyl ethers (1h) and (1i) gave the corresponding methyl substituted cyclohexylaniline 3b and 3c with good to high yields, respectively. The other aryl group of the ethers was converted into the corresponding benzene (65% and 73% yield, respectively) (Table 3, entries 1-2). It is interesting to note that the selectivity of C—O bond cleavage was reversed when the substituent was changed to tert-butyl or phenyl group: cyclohexylaniline (3a) was obtained selectively in high yields, with the other aryl group forming the corresponding arena product tert-butyl benzene (5f) and biphenyl (5g) (Table 3, entries 3-4). It is possible that the solubility might have reversed the selectivity under heterogeneous conditions. 2-Phenoxynaphthalene (11) and 2-(p-tolyloxy)naphthalene (1m) were also successfully cleaved regioselectively, to give the corresponding cyclohexylaniline (3a) and 4-methyl-N-(4-methylcyclohexyl)aniline (3c) in high yields (Table 3, entries 5-6). When methyl and phenyl group were substituted on both phenyl rings, the regioselective cleavage of C—O bond was achieved (Table 3, entry 7) to give 4-methyl-N-(4-methylcyclohexyl)-aniline (3c) as a single nitrogen-containing product in high yield, together with 11% yield of biphenyl and 81% yield of its reduced product, cyclohexylbenzene.
To further investigate the applicability of the catalytic system provided herein, oligomeric phenylene oxides 6 and 7, both containing four C(Ar)—O bonds as polyphenylene oxide (PPO) model compounds, were tested under the standard reaction conditions with increasing sodium borohydride to 2.0 equiv. N-Cyclohexylaniline (3a) and benzene (5a) were obtained with high total yields (123% and 112%, respectively) (
To understand the reaction mechanism, control experiments were carried out, Cyclohexenylphenyl ether (8) was explored as a possible intermediate under the catalytic system; however, it proved otherwise (
Combining these experimental results, a mechanism for this amination reaction is proposed in
It is thus provided a palladium-catalyzed synthesis of aniline derivatives from 4-O-5 linkage lignin model compounds and cheap industrial inorganic chemical ammonia via dual C(Ar)—O bond cleavage. Various symmetrical and unsymmetrical diaryl ethers reacted with ammonia to form the corresponding aniline derivatives and arene products. Furthermore, the method can also be extended to oligomeric phenylene oxide, which provides potential for the valorization of polyphenylene oxide (PPO) wastes.
While the present disclosure has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations, including such departures from the present disclosure as come within known or customary practice within the art and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.
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| Zeng et al., Angewandte Chemie International Edition, (2018), 57(14), p. 3752-3757. |
| Zeng et al., Angewandte Chemie International Edition, (2018), 57(14), p. 3752-3757, supporting information S1-S64. |
