4740-78-7

Basic information

• Product Name: Glycerol formal
• Synonyms: 1,3-Formalglycerol;5-Hydroxy-1,3-dioxane;5-Hydroxy-m-dioxane;m-Dioxan-5-ol;Glycerol F0rmal;Glycerolformal(mixtureof5-Hydroxy-1,3-Dioxaneand4-Hydroxymethyl-1,3-dioxane;Glycerol formal, mixture of isomers, 99+%;GLYCEROL FORMAL/METHYLIDINOGLYCEROL, SERICOSOL N., GLICERINFORMAL0
• CAS NO: 4740-78-7
• Molecular Formula: C₄H₈O₃
• Molecular Weight: 104.10452
• EINECS: 225-248-9
• Product Categories: Pharmaceutical Intermediates;Pesticides
• Mol File: 4740-78-7.mol
• Article Data: 32

Chemical Properties

• Boiling Point: 192-193 °C(lit.)
• Flash Point: 97°C
• Appearance: Clear liquid
• Density: 1.203 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.47E-07mmHg at 25°C
• Refractive Index: n20/D 1.451(lit.)
• Storage Temp.: 0-10°C
• Solubility: Miscible with water and with ethanol (96 per cent).
• PKA: 13.68±0.20(Predicted)
• CAS DataBase Reference: Glycerol formal(CAS DataBase Reference)
• NIST Chemistry Reference: Glycerol formal(4740-78-7)
• EPA Substance Registry System: Glycerol formal(4740-78-7)

Safety Data

• Safety Statements: 23-24/25
• WGK Germany: 3
• F: 3
• Hazardous Substances Data: 4740-78-7(Hazardous Substances Data)

Usage

Chemical Properties

Clear liquid

Uses

Glycerol formal is used as a dye emulsifier and as a cosolvent for drug delivery.

Synthetic route

→ glycerol formal (4740-78-7)

formaldehyd (50-00-0) + glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
With dihydrogen peroxide; nitric acid; cetyltrimethylammonim bromide; ferric nitrate In water at 80℃; for 5h; Reagent/catalyst; Temperature;	A n/a B 95.6%
With hydrogenchloride	A 44% B 56%
With hydrogenchloride In water at 40℃; for 24h; Yields of byproduct given;

Dimethoxymethane (109-87-5) + glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
	A 6% B 94%
With toluene-4-sulfonic acid; lithium bromide In ethyl acetate at 20℃; for 16h; Yield given. Yields of byproduct given;
With toluene-4-sulfonic acid; lithium bromide at 20℃; for 16h; Product distribution; Mechanism; other temperature, other substrates, reactants;

glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + glycolic Acid (79-14-1) + ethyl 2-hydroxyacetate (623-50-7) + diglycerol (627-82-7) + oxiranyl-methanol (556-52-5) + hydroxy-2-propanone (116-09-6) + acrolein (107-02-8)

Conditions	Yield
With pretreated aluminium vanadium phosphate In water at 280℃; under 760.051 Torr; Catalytic behavior; Activation energy; Reagent/catalyst; Temperature;	A n/a B n/a C n/a D n/a E n/a F n/a G n/a H 62%

...Expand

glycerol (56-81-5) + (HCHO)n → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
With toluene-4-sulfonic acid	A 60% B 40%

1,3-dioxan-5-ol benzoate (49784-60-3) → glycerol formal (4740-78-7)

Conditions	Yield
With sodium In methanol; chloroform at 20℃; for 48h;	48%
With potassium hydroxide
With methanol; chloroform; sodium methylate

formaldehyd (50-00-0) + glycerol (56-81-5) → glycerol formal (4740-78-7)

Conditions	Yield
With hydrogen cation	36%
With hydrogenchloride at 0℃;
at 160 - 200℃; im Druckrohr und Destillation des Reaktionsprodukts unter vermindertem Druck;
With hydrogenchloride
With Amberlyst-15 at 100℃; for 1h; Temperature; Reagent/catalyst;

glycerol (56-81-5) + polyoxymethylene → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
With bismuth(lll) trifluoromethanesulfonate In 1,4-dioxane at 40℃; for 0.5h; Sealed tube; Sonication;	A 15% B 28%

formaldehyd (50-00-0) + methanesulfonyl chloride (124-63-0) + glycerol (56-81-5) → glycerol formal (4740-78-7) + 1,3-dioxolan-4-ylmethyl methanesulfonate

Conditions	Yield
With triethylamine Multistep reaction;

formaldehyd (50-00-0) + p-toluenesulfonyl chloride (98-59-9) + glycerol (56-81-5) → glycerol formal (4740-78-7) + (1,3-dioxolan-4-yl)methyl 4-methylbenzenesulfonate (85608-69-1)

Conditions	Yield
With triethylamine Yield given. Multistep reaction. Yields of byproduct given;

hydrogenchloride (7647-01-0) + glycerol (56-81-5) + polyoxymethylene → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
at 130℃;
at 100℃;

sulfuric acid (7664-93-9) + glycerol (56-81-5) + polyoxymethylene → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
at 130℃;
at 100℃;

hydrogenchloride (7647-01-0) + formaldehyd (50-00-0) + glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

1,3,5-Trioxan (110-88-3) + glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
With sodium tetrachloroaurate dihydrate In 1,4-dioxane at 100℃; for 16h; Kinetics; Reagent/catalyst; Temperature; Time; Solvent;

C9H16O4 (1404077-71-9) + 2,2-Dimethyl-propionic acid [1,3]dioxolan-4-ylmethyl ester → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7)

Conditions	Yield
With sodium hydroxide In ethanol at 20℃; for 18h; Inert atmosphere;

glycerol (56-81-5) → glycerol formal (4740-78-7) + 3-methoxy-1-propanal (2806-84-0) + acetaldehyde (75-07-0) + hydroxy-2-propanone (116-09-6) + acrolein (107-02-8)

Conditions	Yield
With H-ZSM5 In water at 340℃; under 760.051 Torr; for 6h; Reagent/catalyst; Inert atmosphere;

formaldehyd (50-00-0) + glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + C9H16O6 + C8H14O6 + C7H12O6

Conditions	Yield
With cesium 12-tungstophosphate at 70℃; Reagent/catalyst;

benzaldehyde (100-52-7) + glycerol (56-81-5) → glycerol formal (4740-78-7)

Conditions	Yield
With zinc-modified strong acid polystyrene cation exchange at 150℃; for 5h;

glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + formic acid (64-18-6)

Conditions	Yield
With dihydrogen peroxide In water at 200℃; for 10h; Catalytic behavior; Reagent/catalyst; Flow reactor; Autoclave; Green chemistry; chemoselective reaction;

glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + formic acid (64-18-6) + acetic acid (64-19-7) + hydroxy-2-propanone (116-09-6)

Conditions	Yield
With dihydrogen peroxide In water at 200℃; for 13h; Flow reactor; Autoclave; Green chemistry; chemoselective reaction;

glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + formic acid (64-18-6) + acetic acid (64-19-7)

Conditions	Yield
With dihydrogen peroxide In water at 200℃; for 21h; Catalytic behavior; Time; Flow reactor; Autoclave; Green chemistry; chemoselective reaction;

glycerol (56-81-5) → 1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + hydroxy-2-propanone (116-09-6)

Conditions	Yield
With alumina; dihydrogen peroxide In water at 200℃; for 4h; Catalytic behavior; Time; Flow reactor; Autoclave; chemoselective reaction;

glycerol formal (4740-78-7) + 1-hexadecylcarboxylic acid (57-10-3) → hexadecanoic acid [1,3]dioxan-5-yl ester (163550-89-8)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide Esterification;	93%

glycerol formal (4740-78-7) + cis-Octadecenoic acid (112-80-1) → (Z)-Octadec-9-enoic acid [1,3]dioxan-5-yl ester (277749-20-9)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide Esterification;	92%

glycerol formal (4740-78-7) + epichlorohydrin (106-89-8) → 1,3-bis[(1,3-dioxan-5-yl)oxy]propan-2-ol (1333247-50-9)

Conditions	Yield
With tetrabutylammomium bromide; water; potassium hydroxide at 20 - 60℃; for 48h; Inert atmosphere; neat (no solvent);	90%

glycerol formal (4740-78-7) + 10-undecenoic acid (112-38-9) → undec-10-enoic acid [1,3]dioxan-5-yl ester (277749-21-0)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide Esterification;	89%

glycerol formal (4740-78-7) + 1-decanoic acid (334-48-5) → decanoic acid [1,3]dioxan-5-yl ester (15180-87-7)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide Esterification;	82%

glycerol formal (4740-78-7) + n-docosanoic acid (112-85-6) → docosanoic acid [1,3]dioxan-5-yl ester (277749-19-6)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide Esterification;	80%

glycerol formal (4740-78-7) + valeric acid (109-52-4) → pentanoic acid [1,3]dioxan-5-yl ester (15180-73-1)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide Esterification;	80%

glycerol formal (4740-78-7) + E-6-amino-9-<1-methyl-2-(tetrahydropyran-2-yloxy)ethenyl>-9H-purine → 9-[2-Bromo-1-([1,3]dioxan-5-yloxy)-1-methyl-2-(tetrahydro-pyran-2-yloxy)-ethyl]-9H-purin-6-ylamine

Conditions	Yield
With N-Bromosuccinimide Ambient temperature;	60%

glycerol formal (4740-78-7) + pivaloyl chloride (3282-30-2) → 2,2-Dimethyl-propionic acid [1,3]dioxolan-4-ylmethyl ester

Conditions	Yield
With 1,3-dioxolane-4-methanol; pyridine In dichloromethane Inert atmosphere;	44%

glycerol formal (4740-78-7) + 2-(2H-tetrazol-5-yl)-N-[4-(trifluoromethyl)phenyl]aniline → 2-(2-(1,3-dioxan-5-yl)-2H-tetrazol-5-yl)-N-(4-(trifluoromethyl)phenyl)aniline

Conditions	Yield
With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0 - 20℃; for 16h; Inert atmosphere;	42.6%

glycerol formal (4740-78-7) + 6-amino-9-(isopropenyl)-9H-purine (159383-03-6) → 9-[2-Bromo-1-([1,3]dioxan-5-yloxy)-1-methyl-ethyl]-9H-purin-6-ylamine

Conditions	Yield
With N-Bromosuccinimide Ambient temperature;	30%

glycerol formal (4740-78-7) → 1,3-dioxan-5-one (87683-81-6)

Conditions	Yield
With Collins reagent	12%
With pyridinium chlorochromate In dichloromethane

glycerol formal (4740-78-7) + carbonochloridic acid, chloromethyl ester (22128-62-7) → chloromethyl (1,3-dioxan-5-yl) carbonate (214543-57-4)

Conditions	Yield
With pyridine In diethyl ether at 0℃; for 20h;	5%

glycerol formal (4740-78-7) + benzoyl chloride (98-88-4) → 1,3-dioxan-5-ol benzoate (49784-60-3)

Conditions	Yield
With quinoline
With pyridine

glycerol formal (4740-78-7) + phenyl isocyanate (103-71-9) → phenyl-carbamic acid-[1,3]dioxan-5-yl ester (92368-06-4)

glycerol formal (4740-78-7) + dimethyl sulfate (77-78-1) → 5-methoxy-1,3-dioxane (99586-36-4)

Conditions	Yield
With potassium hydroxide

glycerol formal (4740-78-7) → 5-chloro-1,3-dioxane (51953-54-9)

Conditions	Yield
With pyridine; thionyl chloride

glycerol formal (4740-78-7) + phosgene (75-44-5) → C5H7ClO4

1,3-dioxolane-4-methanol (5464-28-8) + glycerol formal (4740-78-7) + 2-chloro-1,3,2-dioxaphosphinane (6362-89-6) → 2-(1,3-dioxan-5-yloxy)-1,3,2-dioxaphosphorinane (219133-84-3) + 2-[1,2-(methylenedioxy)propyloxy]-1,3,2-dioxaphosphorinane (219133-79-6)

Conditions	Yield
With triethylamine In diethyl ether at -10 - 20℃; for 1h; phosphorylation; Title compound not separated from byproducts;

Upstream product

• 49784-60-3 1,3-dioxan-5-ol benzoate 
• 56-81-5 glycerol 
• 100-52-7 benzaldehyde 
• 50-00-0 formaldehyd 
• 1404077-71-9 C₉H₁₆O₄ 
• 110-88-3 1,3,5-Trioxan 
• 41128-92-1 O-benzyl-1,3-dioxan-5-ol 
• 7647-01-0 hydrogenchloride 
• 7664-93-9 sulfuric acid 
• 109-87-5 Dimethoxymethane 
• 98-59-9 p-toluenesulfonyl chloride 
• 124-63-0 methanesulfonyl chloride 

Downstream Products

• 32061-16-8 1,3-dioxan-5-yl 4-methylbenzene-1-sulfonate 
• 92368-06-4 phenyl-carbamic acid-[1,3]dioxan-5-yl ester 
• 49784-60-3 1,3-dioxan-5-ol benzoate 

Relevant articles and documents

An efficient method for the refinement of 1,3-methyleneglycerol via bridged acetal exchange and the synthesis of a symmetrically branched glycerol trimer

Acid-catalyzed equilibrium of a mixture of 1,2- and 1,3-methyleneglycerol in 1,4-dioxane affords predominantly the 1,3-isomer via bridged acetal exchange. The minor 1,2-isomer is removed via sequential pivaloylation and tritylation to afford the desired 1,3-isomer in >99.5% purity. A symmetrically branched triglycerol is efficiently synthesized starting from the purified 1,3-isomer. Georg Thieme Verlag Stuttgart · New York.

Mesoporous Zr-SBA-16 catalysts for glycerol valorization processes: Towards biorenewable formulations

Zr-containing SBA-16 materials were utilized in glycerol valorization for the production of esters (via reaction with levulinic acid) and glycerol formal (GF) via acetalisation with paraformaldehyde. The materials were found to be highly active and selective for the production of valuable compounds from glycerol using benign by design solventless protocols which employ mild reaction conditions. Certain materials were also found to be highly reusable and stable under the investigated conditions.

A bifunctional catalyst based on Nb and v oxides over alumina: Oxidative cleavage of crude glycerol to green formic acid

A bimetallic vanadium and niobium oxide catalyst using alumina as support was developed for the conversion of crude glycerol from biodiesel production into formic acid. The high dispersion of the active oxide phase combined with the presence of acid and redox active centers resulted in a high glycerol conversion (>90% for 25 h) with a good selectivity for formic acid (～55%). This process is the first example of a heterogeneous liquid-phase process for the conversion of crude glycerol to formic acid, which is an important chemical intermediate currently derived from petroleum feedstock.

Method for preparing glycerol benzaldehyde

The invention discloses a method for preparing glycerol benzaldehyde. Metal zinc modified strong acid cation exchange resin is used as a catalyst for synthesizing the glycerol benzaldehyde. Owing to modification of metal zinc, the strong acid cation exchange resin has the function of activating aldehydic carbonyl, glycerol conversion rate reaches up to 95% or more, and product yield is 88% or more.