Review

Appl. Chem. Eng., Vol. 30, No. 3, June 2019, 280-289

https://doi.org/10.14478/ace.2019.1036

280

1. Introduction1)

Biomass is a never-ending source of nature that can be utilized in

multiple ways as a feedstock to produce a variety of chemicals and

valuable products. The threatening changes in the global climate be-

cause of the immense use of fossil fuels has shifted the concern of sci-

entists and researchers to look for the alternate renewable sources that

can not only prevent the depletion of the existing resources but also

put a stop or at least minimize the rapid changes in the environ-

ment[1]. Moreover, the cost of the management of biomass waste can

also be reduced if this biomass residue could be converted into handy

† Corresponding Author: Kangwon National University,Department of Chemical Engineering, Samcheok 25913, Republic of KoreaTel: +82-33-570-6543 e-mail: jwemye@kangwon.ac.kr

§ These authors contributed equally to this work.

pISSN: 1225-0112 eISSN: 2288-4505 @ 2019 The Korean Society of Industrial and

Engineering Chemistry. All rights reserved.

materials which are otherwise burdensome to waste management prac-

tices[2]. Currently, only 10% of the crude oil is used for the manu-

facturing of industrial chemicals while the rest of the crude oil goes

to fulfill the needs of transportation fuels. This is the sole reason that

the concern has turned towards the biomass considering it as a poten-

tial source for the production of values added chemicals. The challenge

to keep the biomass conversion processes “green” and cost-effective

has always been a big point to ponder for the researchers[3]. From the

viewpoint of green chemistry, the most valuable renewable feedstock

derived from the plant-based biomass is the carbohydrates[4]. Among

the carbohydrates, hexoses are of significant interest as they can be

converted into the compounds containing five-membered furan ring af-

ter some chemical treatment. Fructose which is obtained by the isomer-

ization of glucose contains this furan ring that can be easily converted

into hydroxymethylfurfural (HMF)[5].

HMF is among one of the significant platform chemicals which are

바이오매스 유래 플랫폼 케미컬들에 대한 효과적인 합성 방법들

이르샤드 모비나§⋅이성우§⋅최은주⋅김정원†

강원대학교 에너지공학부(에너지화학공학전공)(2019년 5월 16일 접수, 2019년 5월 23일 심사, 2019년 5월 27일 채택)

Efficient Synthetic Routes of Biomass-derived Platform Chemicals

Mobina Irshad§, Seongwoo Lee§, Eunju Choi, and Jung Won Kim†

Department of Chemical Engineering, Kangwon National University, Samcheok 25913, Republic of Korea(Received May 16, 2019; Revised May 23, 2019; Accepted May 27, 2019)

록

5-Hydroxymethylfurfural (HMF) 및 그 유도체들인 2,5-furandicarboxylic acid (FDCA)와 2,5-diformylfuran (DFF)는 넓은 응용 범위와 중요한 화학 물질 생산을 위한 좋은 대체 자원으로 인해 “잠자는 거인”으로 인식되고 있다. 본 미니-리뷰 논문은 과거부터 최근까지 이러한 바이오매스 유래 케미컬 플랫폼들에 대한 합성, 전환과 적용에 관해 간략히 소개한다. 많은 과학적 노력들이 자연 환경과 새로운 미래 세대를 보호하기 위해서 재생 가능한 재료들의 최대한 활용을 위한 자연친화적-적용가능한 방법들을 찾기 위한 노력이 지속적으로 행해지고 있다. 최선의 해결책 중 하나는 자연 바이오매스로부터 플랫폼 케미컬을 개발하고 활용하는 것이다.

Abstract5-hydroxymethylfurfural (HMF) and its derivatives, 2,5-furandicarboxylic acid (FDCA) or 2,5-diformylfuran (DFF), are re-garded as the “sleeping giants” owing to their wide range of applications and a good alternative source for the production of significant chemicals in almost all kind of industries. This mini-review briefly covers the aspects related to the syntheses, transformation, and applications for the biomass-derived platform chemicals from past to most recent. Many scientific efforts have continuously been made to find out the environmental benign applicable ways in order to achieve the full advantage of these renewable materials because of not only to protect the globe but also shield the future of new generations. One of the best solutions could be the development and utilization of platform chemicals from the natural biomass.

Keywords: 5-hydroxymethylfurfural (HMF), 2,5-furandicarboxylic acid (FDCA), 2,5-diformylfuran (DFF), Biomass-derived, Platform chemicals

281바이오매스 유래 플랫폼 케미컬들에 대한 효과적인 합성 방법들

Appl. Chem. Eng., Vol. 30, No. 3, 2019

Figure 1. 5-Hydroxymethylfurfural and its derivatives.

obtained from the renewable biomass[6]. U.S. Department of energy

has added HMF and its derivatives, particularly furfural and FDCA in

the list of potential chemicals for future[7] because it can not only be

obtained readily from different sources but also used as a starting ma-

terial in the production of other compounds[8]. The furan ring-contain-

ing compounds that can be derived from HMF are shown in Figure 1.

These include 2,5-diformylfuran (DFF), 2,5-furandicarboxylic acid

(FDCA), 2,5-bis(hydroxymethyl)-furan (BHMF), 2,5-dimethylfuran

(DMF), and levulinic acid. All of these compounds are interlinked to

each other and can be produced by one process or the other in the

transformation reactions. For example, FDCA and DFF are not only

produced by the oxidation of HMF but obtained as a secondary prod-

uct in the chemical conversion of hexoses. FDCA has been employed

in a number of applications such as fungal control agent, melting

agent, photography, pharmaceuticals, rust controlling and as a mono-

mer in particular applications[6,9,10]. Furthermore, FDCA is an ex-

cellent alternative for the terephthalic acid which is widely used in pol-

yester manufacturing[11] and can also be used as a raw material for

the production of succinic acid that is utilized on the large scale in

chemical industries. Moreover, DFF, another important derivative of

HMF has its applications in the fields of polymerization, as inter-

mediate, as a fungicide, ligands preparation, and as a cross-linking

agent[12]. This mini-review focuses on the overview of various meth-

ods which has been employed since long for the conversion of biomass

to HMF and then transformation of HMF to its derivatives particularly

FDCA and DFF. Additionally, the potential applications of FDCA and

DFF have also been outlined to provide the researchers a complete in-

sight into these innovative compounds at one place.

2. 5-Hydroxymethylfurfural - Synthetic Routes

The first paper on the synthesis of HMF by dehydration of sugar in

the acidic environment was published in 1875[13]. Until the middle of

the 20th century, the field of biomass conversion didn’t capture much

interest. In 1951, a review on the topic of furan formation from hexo-

ses was published and gradually this domain caught the attention of

researchers. Since then, the research in the area of conversion of bio-

mass into valued products has gone through several stages from single

phase conventional methods to advanced biphasic and green catalytic

systems. An overview of all these developmental changes with time

can be seen in Figure 2. From past to present, a number of routes have

been proposed for the synthesis of HMF from plants derived biomass

especially carbohydrates. Despite, the method chosen for the conversion,

it has been determined that some factors are influential towards the rate

of transformation of HMF. These factors were first given by Kuster[14]

and are as follows:

⋅Degree of hydrolysis and type of starting material

⋅Amount and nature of the catalyst

⋅Reaction conditions (time, temperature, etc.)

⋅Rate and concentration of the polymerization

⋅Stability of HMF in the given solvent

A number of good reviews have been written[5,8,15,16] constituting

the synthesis of HMF from biomass and each review has its own point

of focus. The current mini-review only summarizes all the possible for-

mation systems of HMF that have been employed in different reaction

conditions. Starting from the biomass which needs some pretreatments

either physical or chemical, the formation systems of biomass to HMF

can broadly be classified in two major categories: autocatalytic systems

and catalytic systems. Autocatalytic systems are defined as the systems

in which a product acts as catalysts to promote the further reaction and

no aid is provided in the form of the external catalyst[15]. These sys-

tems take account of various solvents such as polar protic solvents, po-

lar aprotic solvents, and the solvents which function as the reaction

promoters. Different mechanisms are involved which make a solvent

exhibiting such a performance in a reaction system such as high sol-

ubility of the product, complex formation with solvent, or enhanced ac-

tivity of a specific tautomer[17,18]. Dehydration of carbohydrates by

using catalysts dated back almost a century and since then a lot of

work has been done for the development of sustainable and econom-

ically favorable catalysts. Catalytic systems are generally divided into

homogeneous catalysts, heterogeneous catalysts, metal salt catalysts, and

bi-functional catalysts. Figure 3 provides a general overview of the till

used synthetic routes for the transformation of biomass into 5-hydrox-

ymethylfurfural.

3. Transformation of HMF into Value-added Chemicals

The structure of HMF is said to be the only one of its kind which

makes it the most capable and tempting backbone chemical for the

production of a large number of innovative compounds[19-21]. This

groundbreaking chemical activity of HMF lies in its unique structure

which is the combination of three highly active functional groups such

as -OH group, -CHO group, and a furan ring. By controlling different

reaction conditions, these functional groups can be derivatized into

number of conventional and innovative compounds which are further

282 이르샤드 모비나⋅이성우⋅최은주⋅김정원

공업화학, 제 30 권 제 3 호, 2019

used to produce premium fuels for instance, 2,5-dimethylfuran (DMF)

[22-25], 5-ethoxymethylfurfural (EMF)[26-29], and ethyl levulinate

(EL)[30-32], long chain liquid alkanes (LLA)[33,34], and industrially

valuable chemicals for example levulinic acid (LA)[35-37], 2,5-di-

formylfuran (DFF)[38-41] and 2,5-furandicarboxylic acid (FDCA)

[42-45]. The synthetic route for the production of DFF and FDCA is

represented in Figure 4. The innovation has been created in the syn-

thesis of new compounds by various pre-existing methodologies such

as 2,5-dihydroxymethylfuran (DHMF), 2,5-dihydroxymethyltetrahy-

drofuran (DHMTHF), 1,2,6-hexanetriol (HTO), 1,6-hexanediol (HDO),

1-hydroxyhexane-2,5-dione (HHD), and 3-hydroxymethylcyclopetanone

(HMCPN) have been prepared by the hydrogenation of HMF in the

presence of diverse catalysts. Similarly, maleic anhydride (MA), 5-hy-

droxy-5-(hydroxymethyl)furan-2(5H)-one (HHMFO), and 2,5-furandi-

methylcarboxylate (FDMC) are the products of catalytic oxidation of

HMF. The catalytic conversion of HMF via etherification results in the

Figure 2. Historical background of HMF production.

Figure 3. Summary of conversion systems of biomass to HMF.

Figure 4. Synthesis route of DFF and FDCA from biomass based HMF.

283바이오매스 유래 플랫폼 케미컬들에 대한 효과적인 합성 방법들

Appl. Chem. Eng., Vol. 30, No. 3, 2019

formation of 5-alkoxymethylfurfural (AMF), and 5,5-oxy-(bismethy-

lene)-2 furaldehyde (OBMF). The amination of HMF in the presence

of catalysts produces 5-arylaminomethyl-2-furanmethanol (AAMFM),

1-alkyl-5-hydroxy-2(hydroxymethyl) pyridinium (AHHMP), and 2,5-

furandiamidine dihydrochloride (FDADHC). The catalytic condensation

products of HMF are 5,5-bis(hydroxymethyl)furoin (BHMF), and 5-

(dialkyloxymethyl)-2-furanmethanol (DAMFM). Furthermore, 5-chlor-

omethylfurfural (CMF), 5-alkanoyloxymethylfurfural (AOOMF) and

furfuryl alcohol (FFA) are synthesized by the catalytic halogenation,

esterification and decarbonylation of HMF respectively, under different

reaction conditions.

3.1. Conversion of 5-Hydroxymethylfurfural to 2,5-furandicarboxylic

acid (FDCA)

FDCA was found for the first time in the human urine and later in

the blood plasma. The visual confirmation of the presence of the

FDCA was determined by the Millard reaction indicated by the change

of color (brown) as can be seen in some fruits when exposed to air.

FDCA is a highly stable compound with a melting point of 342 ℃ and

almost insoluble in common solvents except for DMSO. The extra-

ordinary stability of FDCA is attributed to the intermolecular hydrogen

bonding. Various methods have been proposed since now for the syn-

thesis of FDCA but they are broadly classified into three sections[46]:

⋅Hexose derivatives undergo dehydration to give FDCA

⋅2,5-disubstituted furans oxidize to produce FDCA

⋅Different furan derivatives under catalytic conversion reactions

form FDCA

All these methods are dated back to the 18th century and the middle

of the 19th century. Many of them were found to be insufficient to ap-

ply at the industrial level because of non-selectivity, low yields of de-

sired products, the formation of many side products, and severe re-

action conditions[46]. A number of new methods for the synthesis of

FDCA from HMF have been introduced in the late 20th century and

in the 21st century and are reviewed by different researchers[21,47,48].

Oxidation of HMF in the presence of ruthenium catalysts and in the

absence of base was found to be quantitative under moderate

conditions. Different Ru-catalysts were introduced with different sup-

ports though some of them were not of much use because of metal

leaching problems[42,49]. Better results were obtained with the catalyst

produced by incorporating Mg on the surface of carbon and then plati-

num coating on the carbon surface. This catalyst demonstrated much

higher selectivity towards the desired product, i.e. FDCA but the prob-

lem was the same with Mg metal leaching[50]. Furthermore, Pt@CNTs

and Pt nanoparticles were also employed for the oxidative trans-

formation of HMF to FDCA and it was observed that the trans-

formation rate can be enhanced if the O-containing groups are present

on the surface of CNTs[51,52]. Gold nanoparticles with various sup-

ports were used in the base free conditions and high yields (99%) were

obtained[53,54]. Efforts have been made to carry out the oxidation of

HMF to FDCA using earth-abundant metals such as Fe or Co and

cheap metals, for example, a ternary mixture of oxides of Mn/Ce/Cu,

in the presence of additives and optimized reaction conditions[55,56].

Figure 5. Derivatives of FDCA.

Gold-based catalysts were widely studied with different supports and

their reactivity was described as depending on the structure of the cata-

lyst and ratio of the gold nanoparticles with the other metals or sup-

port[57-61]. Carbon and zirconia were also employed as a support with

the ruthenium metal[62] and Kerdi et al. explained the pore diameter

and the surface properties of the carbon-based Ru catalyst for the aque-

ous phase oxidation of HMF to FDCA[63]. Platinum and palladium

supported catalysts also gained interest and demonstrated good results

in various reaction conditions but the consideration of cost-effective-

ness has always been urging the scientists to go deeper finding the

green processes[52,64-68]. Iron-based catalysts and other non-ex-

pensive metals such as cobalt, manganese, vanadium, and copper have

been found a good alternative for the precious metals but their use is

accompanied with the non-selectivity and relatively low product yield

[43,45,55,56,69-71]. Gao, Tianyu et al. have proposed recently numer-

ous methods to bring about the base free aerobic oxidation of 5-HMF

to 2,5-FDCA in water[72-75]. In all protocols, 100% conversion of

HMF were observed yielding > 99% of the desired product FDCA.

Some other research groups performed the HMF conversion reaction

with different metal supported catalysts and reported good results

[51,76-78]. In the last few years, a great deal of research has been ob-

served in proposing different catalytic systems with environmentally

friendly conditions for the HMF conversion into added value products.

These include resins as support, biocatalysts, earth-abundant metals,

precious metals, photo-catalytic irradiation methods and so on

[5,48,79-98]. Moreover, FDCA undergoes all the reaction which are

common for carboxylic acids and therefore can be derivatized further

into different chemicals. One of the most important reactions of FDCA

is polymerization. In addition to these its use is extensive in pharma-

ceutical industries, as an anti-bacterial, antifungal agent, and complxing

agent. Some derivatives of FDCA are shown in Figure 5.

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공업화학, 제 30 권 제 3 호, 2019

3.2. Conversion of 5-hydroxymethylfurfural to 2,5-diformylfuran

(DFF)

2,5-diformylfuran (DFF) is another significant platform compound

that is derived from HMF and can be converted further into a pre-

cursor to many innovative compounds. Some of the important applica-

tions of DFF have been reported in the first half of this mini-review

already. Herein, various synthetic routes for the formation of DFF from

HMF are addressed including catalytic and non-catalytic methods rang-

ing from old to most recent. Ed de Jong et al. reviewed the till date

employed methods in detail for the synthesis of DFF in 2013[21].

Later on, the use of water as a solvent in the formation of DFF from

HMF was reported by many authors and reviewed by Michele Aresta

et al. in 2017[48]. More recent advances in this domain are still in

progress and we have tried to gather them at one place for the sake

of ease of readers. Zhang, H. et al. reported the Photo-catalytic se-

lective oxidation of HMF to DFF on WO3/g-C3N4 composite under ir-

radiation of visible light[94,99]. When it comes to oxidation reactions,

ruthenium has always been a very reliable metal to carry out this

conversion. Therefore, much literature is available on the oxidation of

HMF to DFF using supported ruthenium catalysts[39,40,62,100-106].

Most of the time, the selective oxidation of HMF to DFF has been

studied in the presence of molecular oxygen and toluene as a solvent.

The prepared catalysts were easily recoverable and showed recyclability

over 5 cycles for the oxidation of HMF with more than 95% con-

version and selectivity of HMF and DFF, respectively. In the same

way, manganese oxide supported heterogeneous catalysts have been

proved very consistent and mechanically strong catalysts. Mn has been

found as effective in all forms such as nanoparticles, embedded with

other metals, molecular sieves, or hollow spheres[107-114]. Vanadium

oxide, iron, and copper have been used in numerous ways to produce

benign heterogeneous catalysts and employed for the transformation of

HMF into DFF in various solvents and additives[43,69,115-125].

Several other complex catalytic systems have also been introduced in

recent years, for example, TEMPO which is a well-known catalyst for

the oxidation reactions and have been used since long in homogeneous

catalysis. In current research work, 4-acetamido-TEMPO was used in

the presence of ethyl acetate solvent to synthesize DFF and Fe(NO3)3

and NaCl as co-catalysts[126]. TEMPO and its analogs have low sol-

ubility in ethyl acetate making the separation of the catalyst convenient

after the reaction. At 40 ℃ in 2 hrs, 100% conversion of HMF was

obtained with 89% product yield with a substrate concentration of

0.125 mol/L. In another study, thermally treated partially reduced and

exfoliated graphene oxide was used for the DFF synthesis in the pres-

ence of TEMPO as co-catalyst and the oxygen as the terminal oxidant.

The actual oxidant in this reaction was found to be GO with its re-

duced carboxyl groups which can activate the oxygen to continue the

oxidation reaction. The proposed mechanism explained that the high

reactivity is due to the synergistic effect of -COOH groups and un-

paired electrons at GO edge defects. Under 1atm air pressure and 80

wt% GO loading, 100% HMF conversion was obtained with 99.6%

DFF yield[38]. Liu, Xianxiang et al. proposed a benign method for the

formation of DFF at room temperature[127]. In this conversion, NaNO2

has been used as an oxidant. The solvent was found to have a crucial

effect for this reaction and after testing numerous solvents, trifluoro-

acetic acid gave the best results. Though the conversion of HMF was

not 100%, a high DFF yield was obtained within one hour. Direct and

one-pot synthesis of DFF from carbohydrates such as fructose, glucose,

inulin, and sucrose has been introduced lately by Jun Wang et al. through a promising atom-effective heterogeneous catalyst derived

from the partial carbonization of polyoxometalate based mesoporous

poly(ionic liquid)[128]. Incomplete carbonization spectacularly improved

the acid and oxidation properties, depicting the wholly strengthened ac-

tivity in both the degradation of fructose into 5-hydroxymethylfurfural

(HMF) and oxidation of HMF into DFF with 87.3% yield and turn-over

number (TON) of 77.7.

4. Conclusion and Prospect

In conclusion, the plant-based biomass especially carbohydrates can

be transformed into HMF autocatalytic and catalytic systems. HMF

thus obtained can be further derivatized into a wide range of added

value chemicals via different routes such as transition metal catalysts,

biocatalysts, and homogeneous metal salt catalysts. Among the variety

of chemicals, synthesis of FDCA and DFF from past to recent years

has been discussed in this mini-review and it has been realized that re-

garding lots of potential applications, HMF and its derivatives can be

a tremendous outlet for the chemical industry in future. No doubt,

commercialization of these products is still under trials but things can

be smoothened if the relation between reaction system and work-up

procedure is focused. Countless work is in progress in this domain and

a number of promising results have also been attained in environ-

mentally benign solvents but the shortcomings of using high amounts

of base and high reaction temperatures still need to be solved.

Acknowledgement

This work was supported by 2016 Research Grant from Kangwon

National University (No. 620160135) and the National Research

Foundation (NRF) of Korea Grant funded by the Korean Government

(MSIP) (No. 2016R1D1A3B03934797).

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