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Synthesis of Terephthalic acid From Methane Peng Zhang, Van Nguyen, and John W Frost ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01268 • Publication Date (Web): 24 Aug 2016 Downloaded from http://pubs.acs.org on August 29, 2016

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ACS Sustainable Chemistry & Engineering

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Synthesis of Terephthalic Acid from Methane

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Peng Zhang, Van Nguyen and John W. Frost*

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Department of Chemistry, 578 S. Shaw Lane, Michigan State University,

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East Lansing, MI 48824, United States

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*E-mail: [email protected] Phone: 517-898-9355.

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KEYWORDS: terephthalic acid, biogas, methane, propiolic acid, isoprene

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ABSTRACT: Cycloaddition of propiolic acid with isoprene leads to 4-methyl-1,4-

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cyclohexadiene-1-carboxylic acid in 67% yield. Subsequent reaction of this cycloadduct with O2

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catalyzed by Co(OAc)2/Mn(OAc)2 affords terephthalic acid in a one-pot, cascade oxidation in

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85% yield. Beyond establishing a concise synthesis of terephthalic acid, both propiolic acid and

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isoprene can be synthesized from methane. A route is thus formally established for synthesis of

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biobased terephthalic acid using renewable methane derived from biogas.

13 14 15

INTRODUCTION Terephthalic acid 1 is polymerized with ethylene glycol to form poly(ethylene terephthalate) Recent estimates suggest that 50 x 109 kg/y of terephthalic acid 1 are globally

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PET.

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manufactured.1

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oxidation of p-xylene.2 Although biobased ethylene glycol is commercially available, biobased

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terephthalic acid required for the manufacture of bioPET with 100% renewable carbon content is

Virtually all terephthalic acid 1 is synthesized by the Amoco-MidCentury

ACS Paragon Plus Environment

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not commercially available.3 Synthesis of biobased terephthalic acid 1 has been the focus of

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intense research activity.4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29

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possible use of abundant biogas methane for the synthesis of biobased terephthalic acid 1 is

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examined (Scheme 1). The elaborated strategy is based on a new synthesis of terephthalic acid 1

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that begins with cycloaddition of propiolic acid 2 and isoprene 3 (Scheme 1) to afford 4-methyl-

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1,4-cyclohexadiene-1-carboxylic acid 5 (Scheme 1). A cascade oxidation of cycloadduct 5 leads

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to terephthalic acid 1 (Scheme 1) in a one-pot reaction. Reagents and catalysts needed for

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synthesis of propiolic acid and isoprene from methane are discussed.

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Scheme 1a

In this account,

29 a

30 31 32 33

(a) toluene, 60°C, 67%. (b) Co(OAc)2 (5 mol%), Mn(OAc)2 (5 mol%), N-hydroxysuccinimide (20 mol%), O2, HOAc, 100°C, 85%. (c) TiCl4 (2 mol%), neat, rt, 89%. (d) 5 wt% Pd on C, 240°C, 0.11 bar, 77%. (e) Co(OAc)2 (0.5 mol%), Mn(OAc)2 (0.5 mol%), N-hydroxysuccinimide (10 mol%), O2, HOAc, 100°C, 85%.

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RESULTS and DISCUSSION

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Is switching to methane as the feedstock a viable option for industrial synthesis of terephthalic

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acid 1? In 2013, the U.S. produced 6.9 x 1011 m3 of methane while consuming 7.4 x1011 m3 of

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methane.30 The U.S. had 16 x 1012 m3 of proven methane reserves31,32 (dry natural/shale gas)


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with estimates reaching 81 x 1012 m3 of total methane reserves in 2014.33 Methane hydrate

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reserves of 1,500 x 1012 m3 have been estimated to lie off the coasts of the continental U.S.34,35

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The first successful marine extraction of methane hydrate was from the Nankai Trough offshore

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Japan in 2013.36

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Is use of renewable biogas methane an option for synthesis of terephthalic acid 1? Produced

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from landfill, wastewater treatment, and livestock, biogas production in 2013 was estimated at

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1.2 x 1010 m3 annually.37

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possible.38 This suggests that biogas could supply much of the 4.6 x1010 m3 of methane used by

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the U.S. chemical industry.39 Catalytic upgrading into value-added chemicals is an appealing

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alternative to atmospheric release of biogas methane. Methane is estimated to have a 25-fold

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greater impact on a wt/wt basis relative to CO2 on climate change over a 100-year period.40

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A near-term, fivefold expansion in U.S. biogas production is

Synthesis of terephthalic acid 1 from acrylic acid 4 and isoprene 3 (Scheme 1)41,42 provides an

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intriguing template for synthesis of terephthalic acid 1 from methane.

This synthesis was

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developed43 to take advantage of the availability of biobased acrylic acid 443 and biobased

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isoprene 3.44 While both acrylic acid 4 and isoprene 3 can now be derived from glucose,45,46

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both of these starting materials can also be derived from methane (Scheme 2).

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In the Alder route44 to terephthalic acid 1, solvent-free cycloaddition of acrylic acid 4 with

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isoprene 3 produces 4-methyl-3-cyclohexene-1-carboxylic acid 6 (Scheme 1).43 Vapor phase,

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dehydrogenative aromatization of cyclohexene 6 catalyzed by Pd(0) leads to p-toluic acid

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(Scheme 1).43 In the final step, a modified Amoco-MidCentury oxidation of the p-toluic acid 7

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affords terephthalic acid 1 (Scheme 1).43

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A significant challenge with the synthesis of terepthalic acid 1 from acrylic acid 4 and isoprene

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3 is the formation of byproduct 4-cyclohexanecarboxylic acid 8 (Scheme 1) during the


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aromatization of cyclohexene 6 (Scheme 1).43 Formation of byproduct cyclohexane 8 siphons

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away 20-25% of cycloadduct 6. Loss of the activated allylic H-atom for Pd(0) insertion means

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that aromatization of cyclohexane byproduct 8 likely requires cracking temperatures (>500°C)

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rather than the relatively mild temperatures required (240°C)43 for aromatization of cyclohexene

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6. Reduction in the yield of desired aromatic products during catalytic dehydrogenation of

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cyclohexenes due to formation of unwanted byproduct cyclohexanes is a longstanding problem

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in synthetic chemistry.45,46,47

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Substitution of propiolic acid 2 for acrylic acid 4 was designed to lead to a cyclohexadiene

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intermediate 5 (Scheme 1) that was more reactive towards aromatization relative to cyclohexene

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intermediate 6 (Scheme 1). Cycloaddition of propiolic acid 2 with isoprene 3 afforded 4-methyl-

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1,4-cyclohexadiene-1-carboxylic

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cyclohexadiene-1-carboxylic acid (the meta cycloadduct) in 72% and 24% yield, respectively.

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Crystallization afforded cyclohexadiene 5 in 67% isolated yield. The high conversion in the

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cycloaddition was achieved by using a 25 wt% of propiolic acid 2 in toluene and a 5:1, mol/mol

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ratio of isoprene 3 to propiolic acid 2. Both the elevated concentration of propiolic acid 2 and

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the elevated ratio of isoprene 3 to propiolic acid 2 used in the cycloaddition were important in

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achieving a high conversion in the cycloaddition.

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aromatization of cyclohexadiene intermediate 5 catalyzed by Pd/SiO2 at 240°C/0.11 bar led to an

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88% yield of p-toluic acid 7 with no detectable cyclohexane byproduct 8 formation (entry 1,

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Table 1).

acid

5

(the

para

cycloadduct)

and

5-methyl-1,4-

Vapor phase, catalytic dehydrogenative

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While preparing cyclohexadiene 5 from propiolic acid 2 and isoprene 3, trace amounts of p-

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toluic acid 7 were detected. This prompted examination of catalyst-free oxidative aromatization

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of cyclohexadiene 5 under O2. Highly selective aromatizations were observed in toluene (entry


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2, Table 1), decane (entry 4, Table 1), and o-dichlorobenzene (entry 5, Table 1). A low-yielding

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aromatization was observed in mesitylene at 160°C (entry 3 Table 1). Heating cyclohexadiene 5

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in AcOH at 100°C (entry 6, Table 1) led to a 90% yield of p-toluic acid 7.

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Table 1. Aromatization of 4-Methyl-1,4-cyclohexadiene-1-carboxylic Acid 5

entry

reaction conditions

temp mol% yield

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a

1

b

2

b

3

b

4

b

5

b

6

Pd/SiO2, 0 0 240°C air, 0.11 bar toluene, 40 0 110°C O2, 1 bar, 17h mesitylene, 0 0 160°C O2, 1 bar, 21h decane, 33 0 100°C O2, 1 bar, 17h o-dichlorobenzene 100°C 40 0 O2, 1 bar, 17 h AcOH 0 0 100°C O2, 1 bar, 20 h a Isolated yield. b 1H NMR yield.

88 60 45 67 60 90

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Use of AcOH as solvent, O2 as oxidant, and heating to 100°C are also the reaction conditions

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employed in the Amoco-MidCentury oxidation of p-xylene leading to terephthalic acid 1.2

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Accordingly, reaction of cyclohexadieneyl 5 with O2 using N-hydroxysuccinimide as the chain

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carrier catalyzed by Co(OAc)2 and Mn(OAc)2 led to an 85% yield of terephthalic acid 1 with no

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detectable formation of cyclohexane byproduct 8 (Scheme 1). Terephthalic acid 1 precipitated

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during the oxidation and required only a filtration from the crude reaction mixture. The Ishii

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modification48 of the Amoco-MidCentury oxidation using N-hydroxysuccinimide as the chain

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carrier enabled p-toluic acid to be conveniently oxidized under bench-scale conditions using 1

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atm of O2 in a glass reaction flask.

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employs: (a) elevated pressures of air with sodium bromide as the chain carrier;2 and (b) a

Industrial, large-scale Amoco-MidCentury oxidation


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reaction vessel constructed from titanium, which is resilient towards pressure and resistant to halide corrosion.2

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Conversion of methane into acetylene followed by carboxylation of acetylene (Scheme 2a)

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leads to propiolic acid 1. A variety of different approaches for synthesis of acetylene from

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methane have been commercialized.49 A recently described dehydrodimerization route employs

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a supersonic reactor to achieve yields up to 95% for methane to acetylene conversions (Scheme

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2a).50,51,52 Carboxylation of acetylene (Scheme 2a) has been reported using (4,7-

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diphenylphenanthroline)-bis-(triphenylphoshine)

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diazabicyclo[5.4.0]undec-7-ene (DBU)54 as catalyst. Synthesis of acrylic acid 4 from methane

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requires a longer route.

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CO2) to methanol (Scheme 2b).55,56 Methanol to olefin (MTO) catalysis affords propylene

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(Scheme 2b), frequently as a mixture with ethylene and butylenes.57 Oxidation of propylene then

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affords acrylic acid (Scheme 2b).58

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Scheme 2a

113 114 115 116 117

a

copper(I)

nitrate53

or

1,8-

Methane must be steam-reformed followed by reduction of CO (and

+

(a) 1,500-1,900°C. (b) Cu or DBU. (c) Ni on Al2O3 800°C, 35 bar. (d) CuO/ZnO on Al2O3, 250°C, 50 bar. (e) SAPO-34, 460°C, 1 bar. (f) i) H2O, Fe4BiW2Mo10Si1.35K0.6, 320°C, 2 bar; ii) Mo12V4.6Cu2.2Cr6W2.4 on Al2O3, 220°C. (g) WO3/SiO2 260°C, 35 bar. (h) Fe2O3/Cr2O3/K2CO3, 600°C.


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Propylene and isobutylene derived from methanol using MTO catalysis are the starting point

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for synthesis of isoprene 3 from methane (Scheme 2c). Cross metathesis of propylene with

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isobutylene leads to 2-methyl-2-butene 9 (Scheme 2c).59,60

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modification of the original Phillips Triolefin Process and the currently practiced OCT routes

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to on-purpose synthesis of propylene from 2-butene and ethylene.61 Dehydrogenation of 2-

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methyl-2-butene 9 affords isoprene 3 (Scheme 2c).62 Byproduct ethylene can conceivably be

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converted into the ethylene glycol 10 (Scheme 2c) required for polymerization with terephthalic

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acid 1 to form PET.

This cross metathesis is a

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As with acrylic acid 4, cycloaddition of propiolic acid 2 with isoprene ultimately leads to

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terephthalic acid 1 as the free diacid (Scheme 1). Subsequent polymerization with ethylene

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glycol can afford PET with nontoxic, nonflammable H2O as the byproduct. If cycloaddition had

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required use of an esterified propiolic acid, a subsequent hydrolysis step prior to polymerization

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would require capture and recycling of an alcohol. This would be neither process or atom

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economical. By substituting propiolic acid 2 for acrylic acid 4 as the dienophile for reaction with

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isoprene 3 (Scheme 1), formation of problematic cyclohexane byproduct 8 during cycloadduct

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aromatization is completely eliminated. Aromatization and oxidation of the methyl group are

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also conveniently accomplished in a one-pot, cascade oxidation of the cyclohexadiene 5 (Scheme

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1). Beyond these advantages of propiolic acid 2 as a dienophile in synthesis (Scheme 1) of

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terephthalic acid 1, propiolic acid 2 can be concisely synthesized (Scheme 2a) from methane.

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Synthesis of isoprene 3 from methane (Scheme 2c) simultaneously affords the ethylene required

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for ethylene glycol 10 synthesis. A full accounting will ultimately be required to ascertain the

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energy requirement (methane equivalents) for synthesizing terephthalic acid 1 from methane.


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Nonetheless, with the availability of renewable methane from biogas, a new route has been

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formally established for the manufacture of bioPET with 100% renewable carbon content.

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ASSOCIATED CONTENT

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Supporting Information

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General methods and product analyses for cycloaddition and cascade oxidation reactions. This

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material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

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Corresponding Author

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*E-mail: [email protected] Phone: 517-898-9355.

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Notes

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The authors declare no competing financial interests.

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Financial support was provided by the Coca-Cola Company and NSF (CHE-1213299). Dr.

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Robert Kriegel of the Coca-Cola Company provided helpful discussions.

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ACKNOWLEDGMENT

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For Table of Contents Use Only

Synthesis of Terephthalic Acid from Methane Peng Zhang, Van Nguyen and John W. Frost* SYNOPSIS Reaction of methane-derived propiolic acid with methane-derived isoprene affords a cycloadduct that undergoes a one-pot cascade oxidation to yield terephthalic acid. With use of methane from renewable biogas, a new route to biobased terephthalic acid is established.

HO 2C

CO 2H

CH 4 CH 3OH


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HO 2C

Synthesis of Terephthalic Acid from Methane - ACS Publications

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