4767-03-7

Basic information

• Product Name: 2,2-Bis(hydroxymethyl)propionic acid
• Synonyms: 2,2-DIMETHYLOLPROPIONIC ACID;2,2-BIS(HYDROXYMETHYL)PROPIONIC ACID;DIMETHYLOLPROPIONIC ACID;DMPA(R);2,2-Bis(hydroxymethyl)propanoic acid;2,2-bis(hydroxymethyl)propanoicacid;3-Hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid;3-hydroxy-2-(hydroxymethyl)-2-methyl-propanoicaci
• CAS NO: 4767-03-7
• Molecular Formula: C₅H₁₀O₄
• Molecular Weight: 134.13
• EINECS: 225-306-3
• Product Categories: Organic acids;fine chemicals, specialty chemicals, intermediates, electronic chemical, organic synthesis, Organic acids
• Mol File: 4767-03-7.mol

Chemical Properties

• Melting Point: 189-191 °C(lit.)
• Boiling Point: 167.23°C (rough estimate)
• Flash Point: >150°C
• Appearance: White/Crystalline Powder
• Density: 0.84
• Vapor Density: <1 (vs air)
• Vapor Pressure: 7.26E-07mmHg at 25°C
• Refractive Index: 1.4240 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: H2O: soluble
• Water Solubility: soluble
• Sensitive: Hygroscopic
• Stability: Stable. Hygroscopic.
• Merck: 14,3253
• BRN: 1756385
• CAS DataBase Reference: 2,2-Bis(hydroxymethyl)propionic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 2,2-Bis(hydroxymethyl)propionic acid(4767-03-7)
• EPA Substance Registry System: 2,2-Bis(hydroxymethyl)propionic acid(4767-03-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38-36/37
• Safety Statements: 26-37/39
• WGK Germany: 3
• RTECS: UA2465265
• F: 3-9
• TSCA: Yes
• Hazardous Substances Data: 4767-03-7(Hazardous Substances Data)

Usage

Uses

Used in the Polyurethane Industry:
2,2-Bis(hydroxymethyl)propionic acid is used as a water-based polyurethane chain extender for enhancing the emulsifying properties and stability of the polyurethane produced, resulting in self-emulsifying aqueous polyurethane.
Used in the Coatings and Elastomers Industry:
2,2-Bis(hydroxymethyl)propionic acid is utilized in the preparation of epoxy ester coatings, polyurethane elastomers, and powder coatings, contributing to their improved performance.
Used in the Magnetic Recording and Adhesives Industry:
2,2-Bis(hydroxymethyl)propionic acid is employed in the preparation of magnetic recording materials and adhesives, enhancing their overall quality and functionality.
Used in the Synthesis of Hyperbranched Polymers and Dendrimers:
2,2-Bis(hydroxymethyl)propionic acid is commonly used as an AB2 monomer for the synthesis of hyperbranched (hb) polymers and dendrimers, which have a wide range of applications in various fields.
Used in the Preparation of Water-Soluble Alkyl Resins:
2,2-Bis(hydroxymethyl)propionic acid is also used in the preparation of water-soluble alkyl resins, which find applications in different industries due to their unique properties.
Additionally, 2,2-Bis(hydroxymethyl)propionic acid can be used for the preparation of photosensitive resins and liquid crystal materials, further expanding its utility in the materials science field.

InChI:InChI=1/C5H10O4/c1-5(2-6,3-7)4(8)9/h6-7H,2-3H2,1H3,(H,8,9)/p-1

Synthetic route

3-hydroxy-2-(hydroxymethyl)-2-methylpropanal (18516-18-2) → 2-(hydroxymethyl)-2-methylpropane-1,3-diol (77-85-0) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

Conditions	Yield
With potassium hydroxide

3-acetoxy-2-acetoxymethyl-2-methyl-propionitrile (98960-49-7) → 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

Conditions	Yield
With hydrogenchloride beim Erhitzen des Reaktionsgemisches mit Wasser;
With hydrogenchloride

3-hydroxy-2-hydroxymethyl-2-methylpropionic acid methyl ester (17872-55-8) → 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

Conditions	Yield
With potassium hydroxide

β.β'-dibromo-pivalic acid → 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

Conditions	Yield
With water; lead(II) oxide

β.β'-dichloro-pivalic acid → 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

Conditions	Yield
With sodium hydroxide

3-hydroxy-2-(hydroxymethyl)-2-methylpropanal (18516-18-2) + alcoholic potash → 2-(hydroxymethyl)-2-methylpropane-1,3-diol (77-85-0) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

3-hydroxy-2-(hydroxymethyl)-2-methylpropanal (18516-18-2) → 2,2-bis(hydroxymethyl)propionic acid (4767-03-7)

Conditions	Yield
With dihydrogen peroxide
With sulfuric acid In water Kinetics; Mechanism; Electrolysis;

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 2-Isocyanatoethyl methacrylate (30674-80-7) → C19H28N2O10 (304698-73-5)

Conditions	Yield
Stage #1: 2,2-bis(hydroxymethyl)propionic acid; 2-Isocyanatoethyl methacrylate With dibutyltin dilaurate In tetrahydrofuran at 20℃; Stage #2: With methanol In tetrahydrofuran for 2h;	100%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 1,1-diethoxycyclohexane (1670-47-9) → 3-methyl-1,5-dioxa-spiro-[5,5]undecane-3-carboxylic acid

Conditions	Yield
Stage #1: 1,1-diethoxycyclohexane; toluene-4-sulfonic acid In toluene at 120 - 130℃; Stage #2: 2,2-bis(hydroxymethyl)propionic acid In toluene at 120 - 130℃; for 2.5h;	100%
Stage #1: 1,1-diethoxycyclohexane; toluene-4-sulfonic acid In toluene at 120 - 130℃; Reflux; Stage #2: 2,2-bis(hydroxymethyl)propionic acid In toluene for 2.5h; Reflux;

triethyl borate (150-46-9) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → B(2,2-bis(hydroxymethyl)propionate(3-)) (1188369-88-1)

Conditions	Yield
In ethanol	100%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 2-bromoethanol (540-51-2) → C7H14O5

Conditions	Yield
Stage #1: 2,2-bis(hydroxymethyl)propionic acid With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 2h; Stage #2: 2-bromoethanol In N,N-dimethyl-formamide at 45 - 50℃; for 48h;	100%

bromoacetic acid tert-butyl ester (5292-43-3) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → 2,2-bis(methylol)-3-methyl-3-carboxy-tert-butylacetate (1351112-99-6)

Conditions	Yield
Stage #1: 2,2-bis(hydroxymethyl)propionic acid With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 1h; Stage #2: bromoacetic acid tert-butyl ester In N,N-dimethyl-formamide at 100℃; for 15h;	99%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → α,α-bischloromethyl propionyl chloride (4301-04-6)

Conditions	Yield
With thionyl chloride In N,N-dimethyl-formamide for 32h; Reflux;	99%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + acetyl chloride (75-36-5) → 2,2-bis(acetoxymethyl)propionic acid (17872-58-1)

Conditions	Yield
With dmap; triethylamine In dichloromethane for 0.5h;	98%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 2,2-dimethoxy-propane (77-76-9) → 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid (16837-14-2)

Conditions	Yield
With toluene-4-sulfonic acid In acetone at 20℃; Inert atmosphere;	98%
Stage #1: 2,2-bis(hydroxymethyl)propionic acid; toluene-4-sulfonic acid In benzene Reflux; Stage #2: 2,2-dimethoxy-propane In benzene for 3h;	96.9%
Stage #1: 2,2-bis(hydroxymethyl)propionic acid; toluene-4-sulfonic acid In benzene Reflux; Stage #2: 2,2-dimethoxy-propane In benzene for 1h;	96.9%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + phenylboronic acid (98-80-6) → 5-methyl-2-phenyl-1,3,2-dioxaborinane-5-carboxylic acid (839720-60-4)

Conditions	Yield
In tetrahydrofuran at 20℃; for 3h;	98%
In tetrahydrofuran for 3h;	94%

n-Octylamine (111-86-4) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → 3-Hydroxy-2-hydroxymethyl-2-methyl-N-octyl-propionamide (137607-92-2)

Conditions	Yield
With tertiary amine; (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate	97%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + ortho-bromobenzaldehyde (6630-33-7) → 2-(2-bromophenyl)-5-methyl-1,3-dioxane-5-carboxylic acid

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 80℃;	97%

methanol (67-56-1) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → 3-hydroxy-2-hydroxymethyl-2-methylpropionic acid methyl ester (17872-55-8)

Conditions	Yield
With Amberlyst-15 for 5h; Reflux;	97%
With amberlyst 15 hydrogen form for 22h; Reflux;	97%
With thionyl chloride at 62℃; for 18h;	75%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → C80H130O49

Conditions	Yield
With toluene-4-sulfonic acid at 180 - 185℃; for 10h; Inert atmosphere;	97%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + n-octanoic acid chloride (111-64-8) → C21H38O6

Conditions	Yield
With pyridine In N,N-dimethyl-formamide at 40℃; for 6h; Inert atmosphere;	96%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride (27668-52-6) → dimethyloctadecyl-[3-tris(2-carboxy-3-hydroxy-2-methylpropoxy)silylpropyl]ammonium chloride

Conditions	Yield
In N,N-dimethyl-formamide at 145℃;	96%

copper (II) carbonate hydroxide + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → copper(II) 2,2-bis(hydroxymethyl)propionate

Conditions	Yield
In water at 100℃; for 6h;	96%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 4-bromodeacetyl colchicine → 4-bromo-N-[2,2-bis(hydroxymethyl)propionyl]deacetyl colchicine

Conditions	Yield
Stage #1: 2,2-bis(hydroxymethyl)propionic acid With 1-hydroxybenzotriazol-hydrate; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 4-bromodeacetyl colchicine In N,N-dimethyl-formamide at 20℃;	95.6%

ethanol (64-17-5) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → ethyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate (51689-18-0)

Conditions	Yield
With Dowex at 95℃; for 72h; Fischer–Speier Esterification; Molecular sieve; Inert atmosphere; Schlenk technique;	95.4%
With AMBERLYST 15 Reflux;	91%
With Amberlyst-15 Reflux;	86%
With sulfuric acid for 3h; Heating;	77%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 1,1-dimethoxy-1,2,3,4-tetrahydronaphthalene (105644-28-8) → 5-methyl-3',4'-dihydro-2'H-spiro[1,3-dioxane-2,1'-naphthalene]-5-carboxylic acid (1296664-74-8)

Conditions	Yield
toluene-4-sulfonic acid In toluene at 25 - 30℃; Reflux;	95.28%
Stage #1: 2,2-bis(hydroxymethyl)propionic acid; toluene-4-sulfonic acid In toluene at 25 - 30℃; Stage #2: 1,1-dimethoxy-1,2,3,4-tetrahydronaphthalene In toluene for 4h; Reflux;	95.28%

n-Dodecylamine (124-22-1) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → N-Dodecyl-3-hydroxy-2-hydroxymethyl-2-methyl-propionamide (137607-94-4)

Conditions	Yield
With tertiary amine; (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate	95%

1-aminodecane (2016-57-1) + 2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → N-Decyl-3-hydroxy-2-hydroxymethyl-2-methyl-propionamide (137607-93-3)

Conditions	Yield
With tertiary amine; (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate	95%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 2-(perfluoro-n-octyl)ethylamine (30670-30-5) → N-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluoro-decyl)-3-hydroxy-2-hydroxymethyl-2-methyl-propionamide (137607-96-6)

Conditions	Yield
With tertiary amine; (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate	95%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylamine (30556-86-6) → 3-Hydroxy-2-hydroxymethyl-2-methyl-N-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl)-propionamide (137607-95-5)

Conditions	Yield
With tertiary amine; (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate	94%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) → potassium 2, 2-bis(hydroxymethyl)propanoate

Conditions	Yield
With potassium hydroxide In water at 20℃;	94%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + allyl bromide (106-95-6) → 3-(allyloxy)-2-((allyloxy)methyl)-2-methylpropanoic acid (174822-36-7)

Conditions	Yield
With sodium hydroxide In toluene at 110℃;	92%
With sodium hydroxide In toluene at 110℃;	90.97%
With sodium hydroxide In toluene for 21h; Reflux;	90%
With sodium hydroxide In toluene Reflux;	80%
Stage #1: 2,2-bis(hydroxymethyl)propionic acid With sodium hydroxide In toluene at 110℃; for 0.5h; Stage #2: allyl bromide In toluene Reflux;	77%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 2,2-dimethoxy-propane (77-76-9) + acetone (67-64-1) → 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid (16837-14-2)

Conditions	Yield
With toluene-4-sulfonic acid at 20℃; for 3h;	92%
With toluene-4-sulfonic acid at 20℃; for 12h;	86%
With toluene-4-sulfonic acid

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 1-dodecylbromide (143-15-7) → dodecyl-2,2-bis(methylol)propionate

Conditions	Yield
Stage #1: 2,2-bis(hydroxymethyl)propionic acid With potassium hydroxide In N,N-dimethyl-formamide; acetonitrile at 100℃; for 1h; Stage #2: 1-dodecylbromide In N,N-dimethyl-formamide; acetonitrile	91%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + benzaldehyde dimethyl acetal (1125-88-8) → 5-methyl-2-phenyl-1,3-dioxane-5-carboxylic acid (207850-04-2)

Conditions	Yield
With toluene-4-sulfonic acid In acetone for 2h; Ambient temperature;	90%
With toluene-4-sulfonic acid In acetone	74.02%
With toluene-4-sulfonic acid In acetone at 20℃; for 4h;	64%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + 2,2-dimethoxy-propane (77-76-9) → 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid

Conditions	Yield
Stage #1: 2,2-bis(hydroxymethyl)propionic acid With toluene-4-sulfonic acid In toluene for 0.166667h; Reflux; Stage #2: 2,2-dimethoxy-propane In toluene for 2h;	90%

2,2-bis(hydroxymethyl)propionic acid (4767-03-7) + benzyl bromide (100-39-0) → benzyl 2,2-bis(hydroxylmethyl)propionate (179388-73-9)

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide	89%
With potassium hydroxide In N,N-dimethyl-formamide at 100℃;	89%
With potassium carbonate In N,N-dimethyl-formamide for 7h; Cooling with ice;	80%

Upstream product

• 18516-18-2 3-hydroxy-2-(hydroxymethyl)-2-methylpropanal 
• 98960-49-7 3-acetoxy-2-acetoxymethyl-2-methyl-propionitrile 
• 17872-55-8 3-hydroxy-2-hydroxymethyl-2-methylpropionic acid methyl ester 

Downstream Products

• 17872-55-8 3-hydroxy-2-hydroxymethyl-2-methylpropionic acid methyl ester 
• 103504-66-1 3-(2,3t-diphenyl-acryloyloxy)-2-[(2,3t-diphenyl-acryloyloxy)-methyl]-2-methyl-propionic acid 
• 158665-24-8 benzyl 4-amino>butylate 
• 179388-73-9 benzyl 2,2-bis(hydroxylmethyl)propionate 
• 17872-58-1 2,2-bis(acetoxymethyl)propionic acid 
• 207850-04-2 5-methyl-2-phenyl-1,3-dioxane-5-carboxylic acid 
• 170104-95-7 3-benzyloxy-2-benzyloxymethyl-2-methylpropionic acid 
• 382617-08-5 3-hydroxy-2-hydroxymethyl-2-methyl-N-[3-(naphthalen-1-ylazo)-phenyl]-propionamide 
• 16837-14-2 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid 
• 247142-68-3 2-methyl-2-(benzyloxycarbonyl)-1,3-trimethylene carbonate 

Relevant articles and documents

Kinetics of the electrocatalytic oxidation of 2,2-dimethylolpropionaldehyde

A new method of synthesis 2,2-dimethylolpropionic acid from 2,2-dimethylolpropionaldehyde was put forward. The electrochemical oxidation behavior of 2,2-dimethylolpropionaldehyde has been investigated on a Ti/SnO 2 + Sb2O4/PbO2 electrode by cyclic voltammetry (CV) and stable polarization curves in sulfuric acid. The results showed that it was an irreversible reaction controlled by diffusion. The formation mechanism of 2,2-dimethylolpropionic acid in the sulfuric acid was then proposed and the transfer coefficients of the reaction were calculated. It was concluded that RCHO+OHads→RCHOOHads was the rate-determining step in the electrolysis process. The rate of this step obtained from the assumed process agrees well with experiment.

Method for synthesizing BDO by using 2 - device byproduct 2 hydroxymethyl propionaldehyde and 2 -dimethylolpropionic acid

The invention provides a method for producing BDO by using 2 - byproduct 2 hydroxymethyl propanal, in particular: 2 - hydroxymethyl propanal is condensed under the action of an alkali catalyst, and formaldehyde is condensed to obtain 2 - and 2 dimethylolpropionic aldehyde intermediate which is catalytically oxidized to obtain 2 - and 2 2 - dimethylolpropionic acid. The synthetic route is novel, and by-product BDO hydroxymethyl propanal produced in 2 - process by allyl alcohol method is a starting material and is condensed. 2, 2 Dimethylolpropionic acid is obtained through the oxidation and the like to obtain 2 - and the byproduct of the waste is comprehensively utilized, BDO device three wastes are reduced, a new product can be sold, and the economical efficiency of the device is effectively improved.

Method for isolating polymethyl alkanoic acids and disposal of the resulting wastes

A process for isolating polymethylolalkanoic acids or monomethylolalkanoic acids of the formula (I) where R are identical or different and are each a substituted or unsubstituted hydrocarbon radical or a methylol group, which have been prepared from the corresponding polymethylolalkanals or monomethylolalkanals of the formula (II) where R are as defined above, by oxidation using an aqueous solution of hydrogen peroxide comprises a) carrying out a crystallization followed by a liquid/solid separation (B) to give the acid as first crystallized material (2a) plus mother liquor (3), b) producing further crystallized material (2b) in the mother liquor (3) and separating the resulting mother liquor (3) from the further crystallized material (2b) in a further solid/liquid separation (C), and c) disposing of the resulting mother liquor (3) which has been depleted in the acid.