PRODUCTS

METHYLAL

Methylal is a colorless flammable liquid with a low boiling point, low viscosity and excellent dissolving power.
Methylal has a chloroform-like odor and a pungent taste.
Methylal is the dimethyl acetal of formaldehyde.
Methylal is soluble in three parts water and miscible with most common organic solvents.

CAS Number: 109-87-5
IUPAC name: Methylal
EC Number: 203-714-2
Chemical formula: C3H8O2

Other names: Dimethoxymethane, 109-87-5, METHYLAL, Formal, Methane dimethoxy-, Formaldehyde dimethyl acetal, Dimethyl formal, Anesthenyl, 2 4-Dioxapentane, Methylene dimethyl ether, Bis(methoxy)methane, Methoxymethyl methyl ether, Metylal, Formaldehyde methyl ketal, Formaldehyde dimethylacetal, bis(methyloxy)methane, Methylene glycol dimethylether, 7H1M4G2NUE, CHEBI:48341, Dimethoxy methane, MFCD00008495, HSDB 1820, EINECS 203-714-2, UN1234, UNII-7H1M4G2NUE, Dimethylformal, AI3-16096, CCRIS 9397, Methylene Glycol Dimethyl Ether, Dimethoxy-Methane, Methylenedioxydimethane, EC 203-714-2, CHEMBL15537, (CH3O)2CH2, DTXSID1025564, AKOS000120977, UN 1234, D0637, NS00003248, Q411496, J-520340, InChI=1/C3H8O2/c1-4-3-5-2/h3H2,1-2H, F0001-0207

Synthesis and structure of Methylal:
Methylal can be manufactured by oxidation of methanol or by the reaction of formaldehyde with methanol.
In aqueous acid, Methylal is hydrolyzed back to formaldehyde and methanol.

Due to the anomeric effect, Methylal has a preference toward the gauche conformation with respect to each of the C–O bonds, instead of the anti conformation.
Since there are two C–O bonds, the most stable conformation is gauche-gauche, which is around 7 kcal/mol more stable than the anti-anti conformation, while the gauche-anti and anti-gauche are intermediate in energy.
Since Methylal is one of the smallest molecules exhibiting this effect, which has great interest in carbohydrate chemistry, Methylal is often used for theoretical studies of the anomeric effect.

Applications of Methylal:
Industrially, Methylal is primarily used as a solvent and in the manufacture of perfumes, resins, adhesives, paint strippers and protective coatings.
Another application of Methylal is as a gasoline-additive for increasing octane number.
Methylal can also be used for blending with diesel.

Reagent in organic synthesis of Methylal:
Another useful application of Methylal is to protect alcohols with a methoxymethyl (MOM) ether in organic synthesis.
This can be done using phosphorus pentoxide in dry dichloromethane or chloroform.
This is a preferred method to using chloromethyl methyl ether (MOMCl).

Alternatively, MOMCl can be prepared as a solution in a methyl ester solvent by reacting Methylal and an acyl chloride in the presence of a Lewis acid catalyst like zinc bromide:
MeOCH2OMe + RC(=O)Cl → MeOCH2Cl + RC(=O)(OMe)).

The solution of the reagent can be used directly without purification, minimizing contact with the carcinogenic chloromethyl methyl ether.
Unlike the classical procedure, which uses formaldehyde and hydrogen chloride as starting materials, the highly carcinogenic side product bis(chloromethyl) ether is not generated.

General description of Methylal:
Methylal is a biodegradable dimethyl acetal.
Methylal can be synthesized by acid catalyzed condensation of formaldehyde with methanol.
Methylal is amphiphilic in nature with low viscosity, surface tension and boiling point.

Methylal is a flammable, highly volatile solvent with good dissolving power.
DMM is considered as a potential alternative fuel and fuel additive due to its high oxygen content and its ability to enhance the combustion characteristics of diesel and petrol.
Methylals thermal diffusivity has been determined by photoacoustic method.
Analysis of the molecular structure of DMM by electron diffraction technique shows that it has C2 symmetry with a gauche-gauche conformation.

Applications of Methylal:
Methylal (Formaldehyde dimethyl acetal) may be used in the synthesis of methoxymethyl (MOM) ethers.
Methylal may also be used as an external cross-linker to form microporous polymers.

Methylal is a colorless flammable liquid with a low boiling point, low viscosity and excellent dissolving power.

Methylal is a clear colorless flammable liquid with a low boiling point, low viscosity and an excellent dissolving power.
Methylal has a chloroform-like odor and a pungent taste.

Methylal is the dimethyl acetal of formaldehyde.
Methylal is soluble in three parts water and miscible with most common organic solvents.

Methylal can be manufactured by oxidation of methanol or by the reaction of formaldehyde with methanol.
In aqueous acid, Methylal is hydrolyzed back to formaldehyde and methanol.

Methylal is primarily used as a solvent and in the manufacture of perfumes, resins, adhesives, paint strippers and protective coatings.
Due to the anomeric effect, Methylal has a preference toward the gauche conformation around the C–O bonds, instead of the anti conformation.
Since Methylal is one of the smallest molecules exhibiting this effect, which has great interest in carbohydrate chemistry, Methylal is often used for theoretical studies of the anomeric effect.

Applications of Methylal:
Methylal is a useful synthetic intermediate.
Methylal is used to synthesize the vinyl sulfide nine-membered macrocyclic moiety of griseoviridin.
Methylal is also used to prepare (-)-callystatin A.

Methylal is a versatile chemical with applications in many industries such as paints, perfume, pharmacy, and fuel additives.
DMM can be produced through the reaction of methanol and formaldehyde in the presence of acid catalysts or, directly, through the selective oxidation of methanol over catalysts with redox and acid functionalities.

In terms of sustainability, the so-called bio-methanol derived from syngas obtained via biomass gasification can be used in DMM synthesis.
In this review article, we have condensed and classified the research outputs published over the past decade aimed at producing DMM from methanol over different types of catalysts.

The majority of studies described the reaction of methanol to DMM in a promising way using heterogeneous catalysts in the gas phase for the ease of product and catalyst recovery as well as suitability for continuous processing.
Likewise, the influence of parameters including catalyst component, feed composition, and temperature on the performance of catalysts utilised in DMM production is analysed and discussed.
Further, some perspectives concerning the evolution of potential DMM market with respect to the characteristics of the best catalyst materials for high DMM productivity are expressed.

The present invention discloses a Methylal preparation process, wherein methanol and paraformaldehyde are adopted as raw materials, an acid is adopted as a catalyst, a reaction is performed in an organic solvent in an intermittent reaction manner under stirring to generate Methylal, and separation is performed to obtain the azeotrope of methanol and Methylal or the high-purity Methylal.
According to the present invention, the preparation process has characteristics of rapid reaction and high conversion rate, and is suitable for the organic chemical industry field.

Molar mass: 76.095 g·mol−1
Appearance: Colorless liquid
Odor: Chloroform-like
Density: 0.8593 g cm−3 (at 20 °C)

Melting point: −105 °C (−157 °F; 168 K)
Boiling point: 42 °C (108 °F; 315 K)
Solubility in water: 33% (20 °C)
Vapor pressure: 330 mmHg (20 °C)

XLogP3: 0.2
Hydrogen Bond Acceptor Count: 2
Rotatable Bond Count: 2
Exact Mass: 76.052429494 g/mol

Monoisotopic Mass: 76.052429494 g/mol
Topological Polar Surface Area: 18.5Å²
Heavy Atom Count: 5

Complexity: 12.4
Covalently-Bonded Unit Count: 1
Compound Is Canonicalized: Yes

Consumer Uses of Methylal:
Methylal is used in the following products: coating products, air care products, lubricants and greases, fuels, washing & cleaning products, adhesives and sealants, biocides (e.g. disinfectants, pest control products), fillers, putties, plasters, modelling clay and polishes and waxes.
Other release to the environment of Methylal is likely to occur from: outdoor use and indoor use (e.g. machine wash liquids/detergents, automotive care products, paints and coating or adhesives, fragrances and air fresheners).

Service life of Methylal:
Other release to the environment of Methylal is likely to occur from: outdoor use in long-life materials with high release rate (e.g. tyres, treated wooden products, treated textile and fabric, brake pads in trucks or cars, sanding of buildings (bridges, facades) or vehicles (ships)) and indoor use in long-life materials with high release rate (e.g. release from fabrics, textiles during washing, removal of indoor paints).
Methylal can be found in complex articles, with no release intended: machinery, mechanical appliances and electrical/electronic products (e.g. computers, cameras, lamps, refrigerators, washing machines).

Widespread uses by professional workers of Methylal:
Methylal is used in the following products: lubricants and greases, coating products, explosives, fuels, hydraulic fluids, laboratory chemicals, plant protection products, polymers and washing & cleaning products.

Methylal is used for the manufacture of: .
Other release to the environment of Methylal is likely to occur from: outdoor use and indoor use (e.g. machine wash liquids/detergents, automotive care products, paints and coating or adhesives, fragrances and air fresheners).

Uses at industrial sites of Methylal:
Methylal is used in the following products: fuels, hydraulic fluids, lubricants and greases, polymers, coating products, heat transfer fluids, laboratory chemicals, washing & cleaning products and extraction agents.
Methylal has an industrial use resulting in manufacture of another substance (use of intermediates).

Release to the environment of Methylal can occur from industrial use: in processing aids at industrial sites, of substances in closed systems with minimal release, as an intermediate step in further manufacturing of another substance (use of intermediates) and for thermoplastic manufacture.

Methylal is a low-boiling solvent, stable in the presence of alkalis and mild acids, and to high temperatures and pressures.
Methylal differs from other ethers in that it forms only minute omounts of peroxides.
Methylal will dissolve such synthetic resins as nitrocellulose, cellulose acetate and propionate, ethyl cellulose, vinyl, ''Epons'' and polystyrene, and also many of the natural gums and waxes.
Methylal as a latent solvent is activated by the addition of esters, ketones or alcohols.

Use and Manufacturing of Methylal:
In perfumery; manufacture of artificial resins; reaction medium for Grignard and Reppe reactions.
Methylal is a valuable extraction solvent for pharmaceutical products and a stable, inexpensive solvent for Grignard reactions.
Methylal is stable under alkaline and mild acidic conditions.

Chemical Properties of Methylal:
Methylal is a low-boiling solvent, stable in the presence of alkalis and mild acids, and to high temperatures and pressures.
Methylal differs from other ethers in that it forms only minute omounts of peroxides.

Methylal will dissolve such synthetic resins as nitrocellulose, cellulose acetate and propionate, ethyl cellulose, vinyl, "Epons" and polystyrene, and also many of the natural gums and waxes.
Methylal as a latent solvent is activated by the addition of esters, ketones or alcohols.
Methylals evaporation rate, twice that of acetone, places this ether in a class with such solvents as acetone, methyl acetate and ethyl acetate in resin formulations.

Chemical Properties of Methylal:
Methylal is a colorless liquid with a pungent odor.

Physical properties of Methylal:
Colorless liquid with a pungent, chloroform-like odor

Uses of Methylal:
In perfumery; manufacture of artificial resins; reaction medium for Grignard and Reppe reactions.

Uses of Methylal:
Solvent; fuel; in perfume

Uses of Methylal:
Methylal (Formaldehyde dimethyl acetal) may be used in the synthesis of methoxymethyl (MOM) ethers.
Methylal may also be used as an external cross-linker to form microporous polymers.

Uses of Methylal:
Methylal is a valuable extraction solvent for pharmaceutical products and a stable, inexpensive solvent for Grignard reactions.
Methylal is stable under alkaline and mild acidic conditions.

Reactivity Profile of Methylal:
Methylal, an acetal, is incompatible with strong oxidizing agents and acids .
Breaks down to formaldehyde and methanol in acidic solutions.
A very dangerous fire hazard when exposed to heat, flame or oxidizing agents.
May ignite or explode if heated with oxygen [Lewis].

Chemical Reactivity of Methylal:
Reactivity with Water: No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.

Safety Profile of Methylal:
Moderately toxic by subcutaneous route.
Mildly toxic by ingestion and inhalation.
Can cause injury to lungs, liver, kidneys, and the heart.
A narcotic and anesthetic in high concentrations.

A very dangerous fire hazard when exposed to heat, flame, or oxidzers.
Moderately explosive when exposed to heat or flame.
May ignite or explode when heated with oxygen.
To fight fire, use foam, CO2, dry chemical.
When heated to decomposition it emits acrid smoke and irritating fumes.

Potential Exposure:
Vapors may form explosive mixture with air.
Methylal may be able to form unstable and explosive peroxides.
Heating may cause explosion.

Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions.
Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides.
Hydrolyzes readily in presence of acids to generate aldehydes.

Source:
Methylal is a by-product in the synthesis of trioxane, an intermediate in the manufacture of polyacetal plastics.

Purification Methods of Methylal:
Methylal is a volatile flammable liquid which is soluble in three parts of H2O, and is readily hydrolysed by acids.
Purify Methylal by shaking with an equal volume of 20% aqueous NaOH, stand for 20minutes, dry over fused CaCl2, filter and fractionally distil it through an efficient column.
Store Methylal over molecular sieves.

The increasing concerns regarding exhaust and CO2 emissions from fossil-based transportation fuels have propelled intensive research aimed at finding alternative fuel candidates to realize a clean and renewable fuel system.
In this context, Methylal and its derivatives oxymethylene ethers, a class of oxygenated synthetic fuel, have recently attracted increasing interest because of their fascinating characteristics as a diesel blend compound to significantly reduce soot and nitrogen oxide formation.

At present, Methylal production primarily relies on an established two-step process comprising methanol oxidation and methanol condensation with formaldehyde.
Several new synthetic routes based on methanol or CO2/H2 have been proposed by adopting a reaction coupling strategy, which enables the production of Methylal in one step.

A large variety of bi- and multifunctional catalysts have been developed for each synthetic route.
This Review comprehensively summarizes the latest advances in synthetic approaches, catalyst systems, structure–activity relationships, and reaction mechanism for the catalytic synthesis of Methylal.

Comparisons regarding the features and limitations of different synthetic approaches as well as the related catalytic materials are also provided in order to indicate possible directions for future research, especially on the rational design of catalysts, a vital factor for the commercial production of Methylal.

Methylal (OME1) is a potential blend component for diesel fuel that enables dramatic reductions in pollutant formation.
With current technology, however, the production of OME1 from renewable electricity would be less efficient than other power-to-fuel processes.

We therefore present an alternative process based on a different synthesis route: direct oxidation of methanol.
We use deterministic global optimization to maximize the exergy efficiency of the process.

The problem can be solved globally despite the complexity of the flowsheet and the detailed phase equilibrium and enthalpy models used for most units.
In contrast, only simple models are used for distillation.
The effects of this simplification and that of heat integration are quantified.
The optimized process has a higher exergy efficiency than the benchmark and eliminates all external heat demand.