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

General Description

Methylene Diacetate, also known as Diethyl Malonate, is a chemical compound with 99% purity. It's a transparent liquid and has a wide range of applications. Notably, it’s used in the production of synthetic resins and rubber adhesives, as an intermediate in pharmaceuticals, agricultural chemicals, perfumes, and other organic chemicals. It's also used for dyeing and finishing textiles. When handling it, caution should be taken as it may irritate the eyes, skin, and respiratory tract. Its scientific formula is C7H12O4.

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 
• 625-56-9 Chloromethyl acetate 
• 64-19-7 acetic acid 
• 108-24-7 acetic anhydride 
• 75-09-2 dichloromethane 
• 10534-59-5 tetrabutylammonium acetate 
• 110-88-3 1,3,5-Trioxan 
• 143314-17-4 1-ethyl-3-methylimidazolium acetate 
• 74-95-3 1,1-dibromomethane 
• 462-95-3 formaldehyde diethyl acetal 
• 5539-53-7 Acetyl methanesulfonate 
• 3088-15-1 4,6-dibenzoylresorcinol 
• 109-89-7 diethylamine 

Downstream Products

• 4082-91-1 bis(acetoxymethyl)ether 
• 4082-92-2 bis-acetoxymethoxy-methane 
• 733-07-3 dimesitylmethane 
• 103-84-4 Acetanilid 
• 546-67-8 lead(IV) tetraacetate 
• 3377-21-7 dimethyl 2-methylenemalonate 
• 6606-65-1 n-butyl cyanoacrylate 
• 133978-15-1 2-octyl α-cyanoacrylate 
• 79-10-7 acrylic acid 
• 79-14-1 glycolic Acid 
• 50-00-0 formaldehyd 
• 1222-05-5 galaxolide 
• 897918-85-3 (+/-)-3-chloro-3-(2-bromophenyl)propan-1-ol 
• 897918-81-9 3-(3-bromophenyl)-3-chloropropan-1-ol 

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