Methoxymethylfurfural
Encyclopedia
Methoxymethylfurfural also 5-methoxymethylfuran-2-carbaldehyde, is an organic compound
derived from dehydration of sugars and subsequent etherification with methanol
. This colourless liquid is soluble in a wide range of solvents including lower alcohols. The molecule is a derivative of furan
, containing both aldehyde
and ether
(methoxymethyl) functional groups. MMF has been detected in the leaves and roots of Chilean Jaborosa magellanica (Solanaceae) and is a component of mammary and uterus care herb tea. It has a typical odor suggestive of maraschino cherries. MMF can be made from a wide range of carbohydrate
containing feedstocks including sugar
, starch
and cellulose
using a chemical catalytic process and is a potential "carbon-neutral" feedstock for fuels and chemicals. The company Avantium is currently building a pilot plant to upscale the continuous production of this key YXY building block.
and fructose
. It is formed via the dehydration of the hexoses and subsequent etherification of HMF
. Already in 1936 a batch process was patented for the production of MMF and methyl levulinate
. Bicker reported first order kinetics for the dehydration of fructose, etherification of HMF into 5-methoxymethyl-2-furfural (MMF) and by-products formation in methanol. An MMF yield of 78% at 99% conversion was obtained at 240 °C and a residence time of 2 s. At short residence times, especially at lower temperatures significant amounts of HMF were observed and smaller amount of MMF. The amount of MMF increased with residence time at the cost of the amount of HMF, which indicates that MMF formation goes through HMF. Reactions in various alcohols by Brown et al. led to the formation of the appropriate HMF ether and levulinic acid ester. A number of primary and secondary alcohols was tested, from methanol to 2-butanol. In methanol a yield of 43% MMF was reported in combination with 47% methyl levulinate. Garves has shown that also cellulose is efficiently degraded by alcohols and strong acid-catalysts at 180°C to 200°C within minutes. In methanol methylglucosides
, MMF and methyl levulinates plus methyl formates
are formed in consecutive reactions, accompanied by some humic residues. Avantium, a high throughput company from the Netherlands announced last year that it is building a pilot plant for the upscaling of it’s YXY components of which MMF is a key molecule.
(DMF) and valeric biofuels. Oxidation of MMF results in the formation of 2,5-furandicarboxylic
acid, which has been proposed as a replacement of terephthalic acid
for the production of a wide range of plastics including polyesters and polyamides. The potential applications of furan based building blocks for polymer
applications has been extensively reviewed by Gandini. Patents have appeared that MMF prevents the growth of fungi in leathers, paints, foods and fabrics and that MMF as a part of a much broader spectrum of active compounds is effective against cardio, cerebro-vascular and alzheimers diseases and depression. The addition of MMF and other alkoxymethyl furfurals to a tobacco product has been patented because it acts as a fragrance to provide a sweet flavor in the smoke.
s and in food
items. However, Podesta has shown that MMF is a constituent of the leaves and roots of Chilean Jaborosa magellanica (Griseb.) Dusen (Solanaceae). MMF occurs at concentrations of 5 mg MMF per kg dried roots and leaves. It was also present as a component of the roots of Asparagus cochinchinesis and Asparagus lucidus, however it was assumed that the A. lucidus product had been formed as an artifact from fructose during the isolation process. However, it is claimed that it is one of the ingredients in Mammary & Uterus Care Herb Tea. This tea is made of wild asparagi radix, vaccariae semen, pyrrosia, biota tops and blue citrus peel. Chinese medicine uses them to nourish the Yin, maintain normal breast structure and consistency, remove stagnancy and heat, and to maintain healthy mammary and uterus functions. On the contrary EMF, the ethanol ether of HMF can be found in many alcoholic beverages such as beer and wine, especially those who still contain high sugar levels at the end of the fermentation.
. When analyzed by HPLC it can be quantified by UV. In the picture below the UV spectrum is shown. The peak maximum in methanol is at 279.5 nm (Molar extinction coefficient ε 13854 M−1.cm−1).
The IR sample below was recorded on a Nicolet 6700 FT-IR at room temperature using the liquid film (diamond ATR-cell
) procedure.
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
derived from dehydration of sugars and subsequent etherification with methanol
Methanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...
. This colourless liquid is soluble in a wide range of solvents including lower alcohols. The molecule is a derivative of furan
Furan
Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen. The class of compounds containing such rings are also referred to as furans....
, containing both aldehyde
Aldehyde
An aldehyde is an organic compound containing a formyl group. This functional group, with the structure R-CHO, consists of a carbonyl center bonded to hydrogen and an R group....
and ether
Ether
Ethers are a class of organic compounds that contain an ether group — an oxygen atom connected to two alkyl or aryl groups — of general formula R–O–R'. A typical example is the solvent and anesthetic diethyl ether, commonly referred to simply as "ether"...
(methoxymethyl) functional groups. MMF has been detected in the leaves and roots of Chilean Jaborosa magellanica (Solanaceae) and is a component of mammary and uterus care herb tea. It has a typical odor suggestive of maraschino cherries. MMF can be made from a wide range of carbohydrate
Carbohydrate
A carbohydrate is an organic compound with the empirical formula ; that is, consists only of carbon, hydrogen, and oxygen, with a hydrogen:oxygen atom ratio of 2:1 . However, there are exceptions to this. One common example would be deoxyribose, a component of DNA, which has the empirical...
containing feedstocks including sugar
Sugar
Sugar is a class of edible crystalline carbohydrates, mainly sucrose, lactose, and fructose, characterized by a sweet flavor.Sucrose in its refined form primarily comes from sugar cane and sugar beet...
, starch
Starch
Starch or amylum is a carbohydrate consisting of a large number of glucose units joined together by glycosidic bonds. This polysaccharide is produced by all green plants as an energy store...
and cellulose
Cellulose
Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to over ten thousand β linked D-glucose units....
using a chemical catalytic process and is a potential "carbon-neutral" feedstock for fuels and chemicals. The company Avantium is currently building a pilot plant to upscale the continuous production of this key YXY building block.
Production
Related to the production of furfural, MMF can be produced from C-6 sugars hexoses such as glucoseGlucose
Glucose is a simple sugar and an important carbohydrate in biology. Cells use it as the primary source of energy and a metabolic intermediate...
and fructose
Fructose
Fructose, or fruit sugar, is a simple monosaccharide found in many plants. It is one of the three dietary monosaccharides, along with glucose and galactose, that are absorbed directly into the bloodstream during digestion. Fructose was discovered by French chemist Augustin-Pierre Dubrunfaut in 1847...
. It is formed via the dehydration of the hexoses and subsequent etherification of HMF
Hydroxymethylfurfural
Hydroxymethylfurfural , also 5-furfural, is an organic compound derived from dehydration of certain sugars. This yellow low-melting solid is highly water-soluble. The molecule consists of a furan ring, containing both aldehyde and alcohol functional groups...
. Already in 1936 a batch process was patented for the production of MMF and methyl levulinate
Levulinic acid
Levulinic acid, or 4-oxopentanoic acid, is an organic compound with the formula CH3CCH2CH2CO2H. It is a keto acid. This white crystalline is soluble in water, ethanol, and diethyl ether.-Synthesis and uses:...
. Bicker reported first order kinetics for the dehydration of fructose, etherification of HMF into 5-methoxymethyl-2-furfural (MMF) and by-products formation in methanol. An MMF yield of 78% at 99% conversion was obtained at 240 °C and a residence time of 2 s. At short residence times, especially at lower temperatures significant amounts of HMF were observed and smaller amount of MMF. The amount of MMF increased with residence time at the cost of the amount of HMF, which indicates that MMF formation goes through HMF. Reactions in various alcohols by Brown et al. led to the formation of the appropriate HMF ether and levulinic acid ester. A number of primary and secondary alcohols was tested, from methanol to 2-butanol. In methanol a yield of 43% MMF was reported in combination with 47% methyl levulinate. Garves has shown that also cellulose is efficiently degraded by alcohols and strong acid-catalysts at 180°C to 200°C within minutes. In methanol methylglucosides
Glucoside
A glucoside is a glycoside that is derived from glucose. Glucosides are common in plants, but rare in animals. Glucose is produced when a glucoside is hydrolysed by purely chemical means, or decomposed by fermentation or enzymes....
, MMF and methyl levulinates plus methyl formates
Formic acid
Formic acid is the simplest carboxylic acid. Its chemical formula is HCOOH or HCO2H. It is an important intermediate in chemical synthesis and occurs naturally, most notably in the venom of bee and ant stings. In fact, its name comes from the Latin word for ant, formica, referring to its early...
are formed in consecutive reactions, accompanied by some humic residues. Avantium, a high throughput company from the Netherlands announced last year that it is building a pilot plant for the upscaling of it’s YXY components of which MMF is a key molecule.
Uses
The synthesis of novel biomass-based vinyl polymers from 5-methoxymethyl furfural as the starting material was described by Yoshida. HMF and MMF are also key molecules into the conversion of liquid biofuels. HMF and MMF can be converted to a wide range of mono- and dialkoxymethyl ethers. The compounds can also further converted to 2,5-dimethylfuran2,5-Dimethylfuran
2,5-Dimethylfuran is a heterocyclic compound with the formula 2C4H2O. Although often abbreviated DMF, it should not be confused with dimethylformamide. A derivative of furan, this simple compound is a potential biofuel, being derivable from cellulose.-Production:Fructose can be converted into...
(DMF) and valeric biofuels. Oxidation of MMF results in the formation of 2,5-furandicarboxylic
2,5-Furandicarboxylic acid
2,5-Furandicarboxylic acid , also known as dehydromucic acid, is an oxidized furan derivative. This organic compound was first obtained by Fittig and Heinzelmann in 1876. The first review by Henry Hill was already published in 1901. FDCA has also been detected in human urine. A healthy human...
acid, which has been proposed as a replacement of terephthalic acid
Terephthalic acid
Terephthalic acid is the organic compound with formula C6H42. This colourless solid is a commodity chemical, used principally as a precursor to the polyester PET, used to make clothing and plastic bottles. Several billion kilograms are produced annually...
for the production of a wide range of plastics including polyesters and polyamides. The potential applications of furan based building blocks for polymer
Polymer
A polymer is a large molecule composed of repeating structural units. These subunits are typically connected by covalent chemical bonds...
applications has been extensively reviewed by Gandini. Patents have appeared that MMF prevents the growth of fungi in leathers, paints, foods and fabrics and that MMF as a part of a much broader spectrum of active compounds is effective against cardio, cerebro-vascular and alzheimers diseases and depression. The addition of MMF and other alkoxymethyl furfurals to a tobacco product has been patented because it acts as a fragrance to provide a sweet flavor in the smoke.
As an ingredient in food
Unlike HMF, MMF has not been found to a major extend in natural productNatural product
A natural product is a chemical compound or substance produced by a living organism - found in nature that usually has a pharmacological or biological activity for use in pharmaceutical drug discovery and drug design...
s and in food
Food
Food is any substance consumed to provide nutritional support for the body. It is usually of plant or animal origin, and contains essential nutrients, such as carbohydrates, fats, proteins, vitamins, or minerals...
items. However, Podesta has shown that MMF is a constituent of the leaves and roots of Chilean Jaborosa magellanica (Griseb.) Dusen (Solanaceae). MMF occurs at concentrations of 5 mg MMF per kg dried roots and leaves. It was also present as a component of the roots of Asparagus cochinchinesis and Asparagus lucidus, however it was assumed that the A. lucidus product had been formed as an artifact from fructose during the isolation process. However, it is claimed that it is one of the ingredients in Mammary & Uterus Care Herb Tea. This tea is made of wild asparagi radix, vaccariae semen, pyrrosia, biota tops and blue citrus peel. Chinese medicine uses them to nourish the Yin, maintain normal breast structure and consistency, remove stagnancy and heat, and to maintain healthy mammary and uterus functions. On the contrary EMF, the ethanol ether of HMF can be found in many alcoholic beverages such as beer and wine, especially those who still contain high sugar levels at the end of the fermentation.
Toxicity
It has been claimed that 5-methoxymethyl-2-furaldehyde prevents the growth of fungi in leathers, paints, foods and fabrics. However, the first phase of REACH testing has shown that the oral LD50 value of MMF in Wistar rats was established to exceed 2000 mg/kg body weight. According to the Regulation (EC) No 1272/2008 on classification, labelling and packaging of substances and mixtures, MMF does not have to be classified and has no obligatory labelling requirement for oral toxicity. It was found that MMF gave positive results in the skin irritation test and should be classified as a skin sensitizer.Quantification
MMF can be quantified by using both GC and HPLC. MMF can routinely been analyzed on a GC using for example a Varian VF-WAXms column with a temperature profile up to 250˚C and FID detectorFlame ionization detector
A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia....
. When analyzed by HPLC it can be quantified by UV. In the picture below the UV spectrum is shown. The peak maximum in methanol is at 279.5 nm (Molar extinction coefficient ε 13854 M−1.cm−1).
The IR sample below was recorded on a Nicolet 6700 FT-IR at room temperature using the liquid film (diamond ATR-cell
Attenuated total reflectance
Attenuated total reflectance is a sampling technique used in conjunction with infrared spectroscopy which enables samples to be examined directly in the solid, liquid or gas state without further preparation....
) procedure.