628-51-3

Basic information

• Product Name: METHYLENE DIACETATE, 99
• Synonyms: METHYLENE DIACETATE, 99;aceticacid,methyleneester;diacetoxy-methane;methanediol,diacetate;methylenediacetate;Methyl diacetate;acetic acid methylene diester;Bisacetic acid methylene ester
• CAS NO: 628-51-3
• Molecular Formula: C₅H₈O₄
• Molecular Weight: 132.11462
• EINECS: 200-258-5
• Mol File: 628-51-3.mol
• Article Data: 24

Chemical Properties

• Melting Point: −23 °C(lit.)
• Boiling Point: 164-165 °C(lit.)
• Flash Point: 165 °F
• Appearance: /
• Density: 1.128 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.96mmHg at 25°C
• Refractive Index: n20/D 1.405(lit.)
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• CAS DataBase Reference: METHYLENE DIACETATE, 99(CAS DataBase Reference)
• NIST Chemistry Reference: METHYLENE DIACETATE, 99(628-51-3)
• EPA Substance Registry System: METHYLENE DIACETATE, 99(628-51-3)

Safety Data

• Hazard Codes: Xi
• WGK Germany: 3
• RTECS: AI9075000
• Hazardous Substances Data: 628-51-3(Hazardous Substances Data)

Usage

Uses

Used in Chemical Production:
Methylene Diacetate, 99 is used as an intermediate in the production of synthetic resins and rubber adhesives, contributing to the development of these materials for various applications.
Used in Pharmaceutical Industry:
Methylene Diacetate, 99 is used as an intermediate in the synthesis of pharmaceuticals, playing a crucial role in the development of new drugs and medications.
Used in Agricultural Chemicals:
Methylene Diacetate, 99 is used as an intermediate in the production of agricultural chemicals, helping to create effective products for crop protection and enhancement.
Used in Perfume Industry:
Methylene Diacetate, 99 is used as a component in the formulation of perfumes, adding to the complexity and richness of fragrances.
Used in Dye and Textile Industry:
Methylene Diacetate, 99 is used in dyeing and finishing textiles, improving the colorfastness and quality of fabrics.
Safety Precautions:
When handling Methylene Diacetate, 99, caution should be taken as it may irritate the eyes, skin, and respiratory tract. Proper safety measures and personal protective equipment should be used to minimize exposure and potential health risks.

InChI:InChI=1/C5H8O4/c1-4(6)8-3-9-5(2)7/h3H2,1-2H3

Synthetic route

formaldehyd (50-00-0) + acetic anhydride (108-24-7) → diacetoxymethane (628-51-3)

Conditions	Yield
With solid-phase supported silica chloride at 20℃; for 0.166667h; Neat (no solvent); chemoselective reaction;	90%

dichloromethane (75-09-2) + 1-ethyl-3-methylimidazolium acetate (143314-17-4) → diacetoxymethane (628-51-3) + 1-ethyl-3-methyl-1H-imidazol-3-ium chloride (65039-09-0)

Conditions	Yield
at 50℃; for 16h; Inert atmosphere;	A 86% B n/a

1-ethyl-3-methylimidazolium acetate (143314-17-4) + 1,1-dibromomethane (74-95-3) → diacetoxymethane (628-51-3) + 3-ethyl-1-methyl-1H-imidazol-3-ium bromide (65039-08-9)

Conditions	Yield
at 20℃; for 2h; Inert atmosphere;	A 86% B n/a

formaldehyd (50-00-0) + dimethylacetylene (503-17-3) → diacetoxymethane (628-51-3) + acetic anhydride (108-24-7) + acetic acid (64-19-7) + dimethylglyoxal (431-03-8)

Conditions	Yield
With ozone In dichloromethane at -100℃;	A 7% B 71% C 17% D 5%

4,6-dibenzoylresorcinol (3088-15-1) + diethylamine (109-89-7) → 2-(acetoxymethyl)-4,6-dibenzovlresorcinol + diacetoxymethane (628-51-3)

Conditions	Yield
With paraformaldehyde In acetic acid	A n/a B 68%

3-Methyl-3-buten-2-one (814-78-8) → diacetoxymethane (628-51-3) + acetic anhydride (108-24-7) + meso-3-methyl-3-(3-methyl-1,2,4-trioxolan-3-yl)-1,2,4-trioxolane (131250-90-3) + acetic acid (64-19-7)

Conditions	Yield
With ozone In polyethylene at -75℃; for 3.5h;	A n/a B n/a C 9% D n/a

diazomethane (186581-53-3, 908094-01-9) → diacetoxymethane (628-51-3)

Conditions	Yield
With lead(IV) acetate; benzene

formaldehyd (50-00-0) + bis(acetoxymethyl)ether (4082-91-1) → diacetoxymethane (628-51-3) + bis-acetoxymethoxy-methane (4082-92-2) + 1,7-diacetoxy-2,4,6-trioxa-heptane (27969-30-8)

Conditions	Yield
at 140 - 150℃;

diiodomethane (75-11-6) + silver(I) acetate (563-63-3) → diacetoxymethane (628-51-3)

Chloromethyl acetate (625-56-9) + potassium acetate (127-08-2) → diacetoxymethane (628-51-3)

lead(IV) tetraacetate (546-67-8) + acetic acid (64-19-7) → acetoxyacetic acid (13831-30-6) + methane (34557-54-5) + diacetoxymethane (628-51-3) + methylammonium carbonate (15719-64-9, 15719-76-3, 97762-63-5)

Conditions	Yield
at 120℃;

Chloromethyl acetate (625-56-9) + acetic acid (64-19-7) → diacetoxymethane (628-51-3)

Conditions	Yield
With silver(l) oxide In diethyl ether

formaldehyd (50-00-0) + acetyl chloride (75-36-5) → diacetoxymethane (628-51-3)

Conditions	Yield
With zinc(II) chloride

1,3,5-Trioxan (110-88-3) + acetic acid (64-19-7) → diacetoxymethane (628-51-3)

Conditions	Yield
With acetic anhydride for 15h; Ambient temperature;	4 % Spectr.

3-Methyl-3-buten-2-one (814-78-8) → diacetoxymethane (628-51-3) + acetic anhydride (108-24-7) + acetic acid (64-19-7) + dimethylglyoxal (431-03-8)

Conditions	Yield
With ozone In dichloromethane-d2 at -78℃; Title compound not separated from byproducts;	A 2 % Spectr. B 60 % Spectr. C 15 % Spectr. D 9 % Spectr.

3-Methyl-3-buten-2-one (814-78-8) → diacetoxymethane (628-51-3) + acetic anhydride (108-24-7) + meso-3-methyl-3-(3-methyl-1,2,4-trioxolan-3-yl)-1,2,4-trioxolane (131250-90-3) + dimethylglyoxal (431-03-8)

Conditions	Yield
With ozone In polyethylene at -75℃; for 4h; Further byproducts given;	A 6 % Spectr. B 58 % Spectr. C 8 % Spectr. D 1 % Spectr.

4-propenyl-1,3-dioxane, E-isomer (114988-54-4) + acetic anhydride (108-24-7) → diacetoxymethane (628-51-3) + 1,5-diacetoxy-3-hexene (114988-56-6) + 1,3-diacetoxy-4-hexene (114628-86-3)

Conditions	Yield
With sulfuric acid at 65 - 75℃; for 2.5h; Title compound not separated from byproducts;	A 2.0 g B n/a C n/a

acetic anhydride (108-24-7) + acetonitrile (75-05-8) → formic acid (64-18-6) + diacetoxymethane (628-51-3)

Conditions	Yield
With oxygen In N,N-dimethyl-formamide Product distribution; electrolysis;	A 0.04 % Chromat. B 0.14 % Chromat.

acetic anhydride (108-24-7) + acetonitrile (75-05-8) → diacetoxymethane (628-51-3)

Conditions	Yield
With tetrabutylammomium bromide; oxygen In N,N-dimethyl-formamide Hg cathode, Pt anode, -1.0 V vs SCE; Yield given;

2-Methoxypropene (116-11-0) + dimethylglyoxal (431-03-8) → diacetoxymethane (628-51-3) + acetic anhydride (108-24-7) + meso-3-methyl-3-(3-methyl-1,2,4-trioxolan-3-yl)-1,2,4-trioxolane (131250-90-3)

Conditions	Yield
With ozone In pentane at -78℃;	A 22 % Spectr. B 39 % Spectr. C 12 % Spectr.

sulfuric acid (7664-93-9) + acetic anhydride (108-24-7) + formaldehyde gas → diacetoxymethane (628-51-3)

sulfuric acid (7664-93-9) + acetic anhydride (108-24-7) + polyoxymethylene → diacetoxymethane (628-51-3)

Conditions	Yield
bei Siedetemperatur;

acetic anhydride (108-24-7) + polyoxymethylene + ZnCl2 → diacetoxymethane (628-51-3) + bis(acetoxymethyl)ether (4082-91-1)

Conditions	Yield
at 130℃;

sulfuric acid (7664-93-9) + acetic anhydride (108-24-7) + polyoxymethylene → diacetoxymethane (628-51-3) + bis(acetoxymethyl)ether (4082-91-1) + formaldehyde bis-acetoxymethyl-acetal

Conditions	Yield
at 200℃;

formaldehyd (50-00-0) + sulfuric acid (7664-93-9) + acetic anhydride (108-24-7) → diacetoxymethane (628-51-3)

formaldehyd (50-00-0) + sulfuric acid (7664-93-9) + acetic anhydride (108-24-7) + polyoxymethylene → diacetoxymethane (628-51-3)

Conditions	Yield
bei Siedetemperatur;

diiodomethane (75-11-6) + acetic acid (64-19-7) + acetate_of silver → diacetoxymethane (628-51-3)

Conditions	Yield
at 100℃;

acetic anhydride (108-24-7) + formaldehyde gas → diacetoxymethane (628-51-3)

Conditions	Yield
With sulfuric acid

acetic anhydride (108-24-7) + polyoxymethylene → diacetoxymethane (628-51-3)

Conditions	Yield
With sulfuric acid bei Siedetemperatur;

diacetoxymethane (628-51-3) + N-(2-Benzenesulfonylamino-ethyl)-4-methyl-benzenesulfonamide → 1-Benzenesulfonyl-3-(toluene-4-sulfonyl)-imidazolidine

Conditions	Yield
With boron trifluoride diethyl etherate In acetic acid at 80℃; for 1h;	95%

diacetoxymethane (628-51-3) + rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene (87751-69-7) → dimethyl 2-[(E)-(S)-1,3-diphenylallyl]-malonate (95071-02-6, 96482-67-6, 131065-36-6, 148553-10-0, 96482-64-3)

Conditions	Yield
With N,O-bis-(trimethylsilyl)-acetamide; (1R,2S)-2-dimethylamino-1-(ferrocenylthio)-1-phenylpropane; potassium acetate In dichloromethane at 20℃; for 20h;	88%

diacetoxymethane (628-51-3) + acetic anhydride (108-24-7) → formaldehyd (50-00-0)

Conditions	Yield
With solid-phase supported silica chloride In methanol at 20℃; for 0.5h;	88%

diacetoxymethane (628-51-3) + rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene (87751-69-7) → (R)-methyl 2-carbomethoxy-3,5-diphenylpent-4-enoate (95071-02-6, 96482-64-3, 131065-36-6, 148553-10-0, 96482-67-6)

Conditions	Yield
With N,O-bis-(trimethylsilyl)-acetamide; (S)-2-benzylideneamino)-1-(ferrocenylthio)-3-methylbutane; potassium acetate In dichloromethane at 20℃; for 90h;	85%

4-vinylbenzyl chloride (1073-67-2) + diacetoxymethane (628-51-3) → (+/-)-3-chloro-3-(4-chlorophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	84%

diacetoxymethane (628-51-3) + 2'-ethylhexyl cyanoacetate (13361-34-7) → 2-ethylhexyl α-cyanoacrylate

Conditions	Yield
With piperazine; dodecylbenzene-sulphonic acid at 120 - 130℃; for 2h;	84%

diacetoxymethane (628-51-3) + 2-octyl cyanoacetate (52688-08-1) → 2-octyl α-cyanoacrylate

Conditions	Yield
With N,N-dimethylmethyleneammonium ion; dodecylbenzene-sulphonic acid at 120 - 130℃; for 2h;	83%

styrene (292638-84-7) + diacetoxymethane (628-51-3) → (+/-)-3-bromo-3-phenylpropan-1-ol

Conditions	Yield
With boron trifluoride; tetrabutylammomium bromide at -78 - 20℃;	82%

diacetoxymethane (628-51-3) → acetoxymethyl bromide (590-97-6)

Conditions	Yield
With trimethylsilyl bromide; zinc(II) chloride Ambient temperature;	81%

styrene (292638-84-7) + diacetoxymethane (628-51-3) → (+/-)-3-chloro-3-phenylpropan-1-ol (18775-64-9)

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	79%

para-fluorostyrene (405-99-2) + diacetoxymethane (628-51-3) → (+/-)-3-chloro-3-(4-fluorophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	79%

1-bromo-4-ethenyl-benzene (2039-82-9) + diacetoxymethane (628-51-3) → (+/-)-3-chloro-3-(4-bromophenyl)propan-1-ol (908260-10-6, 219745-24-1)

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	79%

diacetoxymethane (628-51-3) + 3-fluorostyrene (350-51-6) → 3-chloro-3-(3-fluorophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	76%

1-ethenyl-4-methylbenzene (622-97-9) + diacetoxymethane (628-51-3) → 3-chloro-3-p-tolylpropan-1-ol (219745-20-7)

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	71%

diacetoxymethane (628-51-3) + cyanoacetic acid 6-(2-cyanoacetoxy)hexyl ester (75750-46-8) → 1,6-hexanediol-bis(2-cyanoacrylate)

Conditions	Yield
With 2,2'-dihydroxy-5,5'-dimethyl-3,3'-di-tert-burtyl-1,1'-diphenylmethane; dodecylbenzene-sulphonic acid; (RS)-2-methylpiperazine at 110℃; for 2h;	71%

diacetoxymethane (628-51-3) + cyanoacetic acid octadecyl ester (71888-58-9) → octadecyl cyanoacrylate

Conditions	Yield
With 1,3,5-trimethyl-1,3,5-triazacyclohexane; 2,6-di-tert-butyl-4-methyl-phenol; dodecylbenzene-sulphonic acid at 125℃;	70%

diacetoxymethane (628-51-3) + N,N'-ethanediyl-bis-benzamide (644-33-7) → 1,3-dibenzoyl-imidazolidine (49738-18-3)

Conditions	Yield
With boron trifluoride diethyl etherate In acetic acid at 80℃; for 3h;	67%

diacetoxymethane (628-51-3) + cyanoacetoxymethyltrimethylsilane → (α-cyanoacryloyloxymethyl)trimethylsilane

Conditions	Yield
With dodecylbenzene-sulphonic acid; (RS)-2-methylpiperazine at 120 - 130℃; for 2h;	66%

diacetoxymethane (628-51-3) + 2-But-3-enyl-2-(5-hydroxy-4-oxo-4H-pyran-2-ylmethyl)-malonic acid dimethyl ester (87057-52-1) → (1R,6R,8S)-10-Acetoxy-9-oxo-12-oxa-tricyclo[6.3.1.01,6]dodec-10-ene-3,3-dicarboxylic acid dimethyl ester (87057-59-8)

Conditions	Yield
at 110℃; for 48h;	65%

3-methylstyrene (100-80-1) + diacetoxymethane (628-51-3) → 3-chloro-3-m-tolylpropan-1-ol (219745-19-4)

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	63%

diacetoxymethane (628-51-3) + 3-Chlorostyrene (2039-85-2) → 3-chloro-3-(3-chlorophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	62%

diacetoxymethane (628-51-3) + 3-bromostyrene (2039-86-3) → 3-(3-bromophenyl)-3-chloropropan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	59%

diacetoxymethane (628-51-3) + 2-bromostyrene (2039-88-5) → (+/-)-3-chloro-3-(2-bromophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	47%

diacetoxymethane (628-51-3) + 2-fluorostyrene (394-46-7) → (+/-)-3-chloro-3-(2-fluorophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	45%

diacetoxymethane (628-51-3) + 2-chlorostyrene (2039-87-4) → 3-chloro-3-(2-chlorophenyl)propan-1-ol

Conditions	Yield
With boron trifluoride at -78 - 20℃; Prins reaction;	44%

Upstream product

• 50-00-0 formaldehyd 
• 4082-91-1 bis(acetoxymethyl)ether 
• 814-78-8 3-Methyl-3-buten-2-one 
• 75-09-2 dichloromethane 
• 10534-59-5 tetrabutylammonium acetate 
• 110-88-3 1,3,5-Trioxan 
• 108-24-7 acetic anhydride 
• 143314-17-4 1-ethyl-3-methylimidazolium acetate 
• 74-95-3 1,1-dibromomethane 
• 5539-53-7 Acetyl methanesulfonate 
• 462-95-3 formaldehyde diethyl acetal 
• 3088-15-1 4,6-dibenzoylresorcinol 
• 109-89-7 diethylamine 
• 75-36-5 acetyl chloride 

Downstream Products

• 4082-91-1 bis(acetoxymethyl)ether 
• 4082-92-2 bis-acetoxymethoxy-methane 
• 590-97-6 acetoxymethyl bromide 
• 17356-23-9 bis-acetylated 1,4-butenediol 
• 84223-09-6 acetoxymethyl β-acetoxypropionate 
• 60-35-5 acetamide 
• 100-97-0 hexamethylenetetramine 
• 631-61-8 ammonium acetate 
• 1222-05-5 galaxolide 
• 133978-15-1 2-octyl α-cyanoacrylate 
• 6606-65-1 n-butyl cyanoacrylate 
• 3377-21-7 dimethyl 2-methylenemalonate 
• 79-10-7 acrylic acid 
• 79-14-1 glycolic Acid 

Relevant articles and documents

Reaction pathways at the initial steps of trioxane polymerisation

Cleavage and (re)formation of oxymethylene moieties are essential steps during the build-up of polyoxymethylene (POM), a technically relevant high-performance polymer. To reveal how the catalyst accomplishes the cleavage of oxymethylene moieties, the kinetics of the ring-opening of trioxane was studied. Thereby insights into the initial phase of the growth of oxymethylene chains were obtained. The chain length of short oligomers was controlled with acetic anhydride as transfer agent. With a high ratio of acetic anhydride to trioxane, the first homologues of the series, trioxymethylene diacetate, dioxymethylene diacetate and monooxymethylene diacetate were obtained in excellent yield. The homologues show distinct features in the NMR and IR spectra that were related to their reactivity during chain propagation. Formation of intermediate hemi-acetal oxonium moieties is suggested to be a key step in the reaction pathway. Such molecular level insight may be a crucial factor for further tailoring production and properties of polyoxymethylene as well as introducing oligomeric oxymethylene diacetates to new application fields.

Process for preparing 1,1-disubstituted ethylenic monomers

The present invention relates to a process for preparing 1,1-disubstituted ethylene monomers having general formula (I) from a compound of general formula (II) and an active methylene compound of general formula (III) using a catalytic amount of an ammonium or iminium salt in homogeneous phase or supported on a solid substrate. Said process allows the direct synthesis of the monomers and finds application in the preparation of a wide variety of monomers. The products obtained are reactive monomers of high purity which find application in the field of fast curing adhesives.

PROCESS FOR PREPARING V- TI-P CATALYSTS FOR SYNTHESIS OF 2,3-UNSATURATED CARBOXYLIC ACIDS

The invention relates to a catalyst composition comprising a mixed oxide of vanadium, titanium, and phosphorus. The titanium component is derived from a water-soluble, redox-active organo-titanium compound. The catalyst composition is highly effective at facilitating the vapor-phase condensation of formaldehyde with acetic acid to generate acrylic acid, particularly using an industrially relevant aqueous liquid feed. Additionally, the catalyst composition is catalytically active towards the formation of acrylic acid from methylene diacetate and methacrylic acid from methylene dipropionate; both reactions are carried out with high space time yields.

HYDROCARBOXYLATION OF METHYLENE DIPROPIONATE IN THE PRESENCE OF PROPIONIC ACID AND A HETEROGENEOUS CATALYST

Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of methylene dipropionate in the presence of a solid acid catalyst and propionic acid. This invention discloses hydrocarboxylations and corresponding glycolic acid separations wherein the propionic acid stream is readily removed from the glycolic acid and the propionic acid is recycled.

HYDROCARBOXYLATION OF FORMALDEHYDE IN THE PRESENCE OF A HIGHER ORDER CARBOXYLIC ACID AND HETEROGENEOUS CATALYST

Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of formaldehyde in the presence of a solid acid catalyst and a carboxylic acid. This invention discloses hydrocarboxylations and corresponding glycolic acid separations wherein the glycolic acid stream is readily removed from the carboxylic acid and the carboxylic acid is recycled.

HYDROCARBOXYLATION OF METHYLENE DIPROPIONATE IN THE PRESENCE OF A PROPIONIC ACID AND A HOMOGENEOUS CATALYST

Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of methylene dipropionate in the presence of a homogeneous acid catalyst and propionic acid. This invention discloses hydrocarboxylations and corresponding homogeneous acid catalyst and glycolic acid separations. The homogeneous acid catalyst is readily separated from the hydrocarboxylation reaction effluent and recycled and the propionic acid is readily removed from the glycolic acid and the propionic acid is recycled

HYDROCARBOXYLATION OF FORMALDEHYDE IN THE PRESENCE OF A HIGHER ORDER CARBOXYLIC ACID AND A HOMOGENEOUS CATALYST

Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of formaldehyde in the presence of a homogeneous acid catalyst and a carboxylic acid. This invention discloses hydrocarboxylations and corresponding homogeneous acid catalyst and glycolic acid separations. The homogeneous acid catalyst is readily separated from the hydrocarboxylation reaction effluent and recycled and the carboxylic acid is readily removed from the glycolic acid and the carboxylic acid is recycled.

Process for preparing esters and organic halides

A process for preparing esters and organic halides, which comprises reacting - a salt having a melting point of less than 100°C (at 1 bar) and of the formula ???????? (K+)n X (COO-)n, in which K+ is an organic cation, X (COO-)n is an organic anion having an n-valent organic group X which is substituted by n carboxylate groups COO-, and n is 1, 2 or 3, - with an organic halogen compound (Hal)mY, in which Hal is a halogen atom, Y is an m-valent organic group, and m is 1, 2 or 3, to give an ester and a halide K+ Hal-.

Chemoselective protection and deprotection of aldehydes using solid supported reagent (Silica Chloride) under solvent-free conditions

Silica chloride, a heterogeneous catalyst, has been found to be an efficient catalyst for the protection of aldehydes as acylals under solvent-free conditions, and deprotection of acylals to aldehydes in methanol as a solvent occurred. The reaction takes a shorter time and ensures good to excellent yield of the products.