15484-46-5

Basic information

• Product Name: 2-Propenoic acid,2-(hydroxymethyl)-, methyl ester
• Synonyms: Acrylicacid, 2-(hydroxymethyl)-, methyl ester (8CI);Hydracrylic acid, 2-methylene-,methyl ester (7CI);Methyl 2-hydroxymethyl-2-propenoate;Methyl a-(hydroxymethyl)acrylate
• CAS NO: 15484-46-5
• Molecular Formula: C₅H₈O₃
• Molecular Weight: 116.1152
• Product Categories: Building Blocks/Intermediates
• Mol File: 15484-46-5.mol
• Article Data: 66

Chemical Properties

• Boiling Point: 184.807 °C at 760 mmHg
• Flash Point: 75.041 °C
• Appearance: /
• Density: 1.086 g/cm³
• Vapor Pressure: 0.205mmHg at 25°C
• Refractive Index: 1.438
• Storage Temp.: 2-8°C
• PKA: 13.66±0.10(Predicted)
• CAS DataBase Reference: 2-Propenoic acid,2-(hydroxymethyl)-, methyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Propenoic acid,2-(hydroxymethyl)-, methyl ester(15484-46-5)
• EPA Substance Registry System: 2-Propenoic acid,2-(hydroxymethyl)-, methyl ester(15484-46-5)

Safety Data

• RIDADR: NA 1993 / PGIII
• WGK Germany: 1
• Hazardous Substances Data: 15484-46-5(Hazardous Substances Data)

Usage

InChI:InChI=1/C5H8O3/c1-4(3-6)5(7)8-2/h6H,1,3H2,2H3

Synthetic route

formaldehyd (50-00-0) + acrylic acid methyl ester (292638-85-8) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In 1,4-dioxane; water at 20℃; for 9h; Baylis-Hillman reaction;	90%
With 1,4-diaza-bicyclo[2.2.2]octane In methanol at 20℃; for 9h; Baylis-Hillman reaction;	90%
With 1,4-diaza-bicyclo[2.2.2]octane In 1,4-dioxane; water at 20℃; for 12h;	90%

formaldehyd (50-00-0) + (methyloxycarbonylmethyl)triphenylphosphonium bromide (1779-58-4) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With potassium carbonate In water at 10 - 20℃; for 6h;	85%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + acrylic acid methyl ester (292638-85-8) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With formaldehyd; paraformaldehyde In diethyl ether; nitrogen	77%

formaldehyd (50-00-0) + trimethyl phosphonoacetate (5927-18-4) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
Stage #1: formaldehyd With phosphoric acid In water at 90℃; for 5h; Stage #2: trimethyl phosphonoacetate With potassium carbonate In water at 35 - 40℃; for 0.9h;	62%
With potassium carbonate In water at 20℃; for 1h;	55%
With potassium carbonate In water at 20℃; for 2h;	44%
With potassium carbonate at 30 - 35℃; for 1h;

formaldehyd (50-00-0) + acrylic acid methyl ester (292638-85-8) → methyl 2-hydroxymethylacrylate (15484-46-5) + dimethyl 2,2′-[oxybis(methylene)]diacrylate (109669-53-6)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane at 95℃; for 4h;	A 23% B 60%

formaldehyd (50-00-0) + trimethyl phosphonoacetate (5927-18-4) → methyl 2-hydroxymethylacrylate (15484-46-5) + acrylic acid methyl ester (292638-85-8)

Conditions	Yield
With potassium carbonate In water at 23℃;	A 56% B n/a

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + cyclohexanol formaldehyde hemiacetal + acrylic acid methyl ester (292638-85-8) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
In cyclohexanol	45%

formaldehyd (50-00-0) + ethyl acrylate (140-88-5) → methyl 2-hydroxymethylacrylate (15484-46-5) + dimethyl 2,2′-[oxybis(methylene)]diacrylate (109669-53-6)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane for 19h; Heating;	A n/a B 13%

2-acetoxymethyl-acrylic acid (89533-83-5) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With methanol; sulfuric acid

methanol (67-56-1) + propargyl alcohol (107-19-7) + tetracarbonyl nickel (13463-39-3, 71564-36-8) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
(i) AcOH, (ii) /BRN= 506003/, (iii) H2SO4; Multistep reaction;

methanol (67-56-1) + ethyl 2-(hydroxymethyl)acrylate (10029-04-6) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With potassium carbonate at 20℃; for 4h;

methanol (67-56-1) + carbon monoxide (201230-82-2) + propargyl alcohol (107-19-7) → methyl 2-hydroxymethylacrylate (15484-46-5) + methyl α-methoxymethylacrylate (25328-81-8)

Conditions	Yield
With methanesulfonic acid; palladium diacetate; diphenyl-(6-methyl-pyridin-2-yl)phosphine In 1,2-dichloro-ethane at 50℃; under 22801.5 Torr; for 3h; Catalytic behavior; Inert atmosphere; Schlenk technique; Autoclave; regioselective reaction;	A 23.8 %Chromat. B 71.4 %Chromat.

methanol (67-56-1) + propargyl alcohol (107-19-7) → methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With methanesulfonic acid; palladium diacetate; diphenyl-(6-methyl-pyridin-2-yl)phosphine In 1,2-dichloro-ethane at 50℃; under 22801.5 Torr; for 3h; Catalytic behavior; Temperature; Pressure; Solvent; Inert atmosphere; Schlenk technique; Autoclave; regioselective reaction;	95.2 %Chromat.

methanol (67-56-1) + propargyl alcohol (107-19-7) → methyl 4-hydroxy-2-butenoate (29576-13-4) + methyl 2-hydroxymethylacrylate (15484-46-5) + methyl α-methoxymethylacrylate (25328-81-8)

Conditions	Yield
With methanesulfonic acid; palladium diacetate; diphenyl-(6-methyl-pyridin-2-yl)phosphine In 1,2-dichloro-ethane at 60℃; under 22801.5 Torr; for 20h; Catalytic behavior; Inert atmosphere; Schlenk technique; Autoclave; regioselective reaction;	A 6.1 %Chromat. B 21.6 %Chromat. C 72.2 %Chromat.
With methanesulfonic acid; palladium diacetate; diphenyl-(6-methyl-pyridin-2-yl)phosphine In 1,2-dichloro-ethane at 60℃; under 22801.5 Torr; for 3h; Catalytic behavior; Inert atmosphere; Schlenk technique; Autoclave; regioselective reaction;	A 5.9 %Chromat. B 85.6 %Chromat. C 8.5 %Chromat.

methanol (67-56-1) + propargyl alcohol (107-19-7) → methyl 4-hydroxy-2-butenoate (29576-13-4) + methyl 2-hydroxymethylacrylate (15484-46-5)

Conditions	Yield
With methanesulfonic acid; palladium diacetate; diphenyl-(6-methyl-pyridin-2-yl)phosphine In 1,2-dichloro-ethane at 50℃; under 22801.5 Torr; for 3h; Catalytic behavior; Inert atmosphere; Schlenk technique; Autoclave; regioselective reaction;	A 5.3 %Chromat. B 94.7 %Chromat.

methyl 2-hydroxymethylacrylate (15484-46-5) + acetyl chloride (75-36-5) → methyl 2-(1-acetoxymethyl)acrylate (30982-08-2)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; for 18h; Schlenk technique; Inert atmosphere;	100%
With pyridine In dichloromethane at -12 - 20℃; for 3h; Inert atmosphere;	85%
With triethylamine In dichloromethane at 0 - 20℃;	71%
With pyridine In diethyl ether at 20℃; for 0.5h; Inert atmosphere;	44%
With pyridine In dichloromethane at 0 - 20℃; for 24h;

triethylsilyl chloride (994-30-9) + methyl 2-hydroxymethylacrylate (15484-46-5) → C11H22O3Si (1189797-29-2)

Conditions	Yield
With dmap; triethylamine In dichloromethane	100%

methyl 2-hydroxymethylacrylate (15484-46-5) → dimethyl 3,3'-oxy(2E,2'E)-bis(2-methylacrylate)

Conditions	Yield
With Co(dmgBF2)2(THF)2; hydrogen In benzene at 50℃; for 24h;	100%

methyl 2-hydroxymethylacrylate (15484-46-5) → methyl 3-hydroxy-2-methylpropanoate (64809-29-6)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In ethyl acetate at 20℃;	97%
With bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; N(1)-(4-butylphenyl)-N(2)-(4-((11bS)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yloxy)phenyl)phthalamide; hydrogen In dichloromethane at 20℃; under 37503.8 Torr; for 20h; Autoclave;
With bis(norbornadiene)rhodium(l)tetrafluoroborate; C50H44N3O2P; C112H112N8O8Zn; hydrogen In dichloromethane at 25℃; under 7500.75 Torr; for 16h;
With bis(norbornadiene)rhodium(l)tetrafluoroborate; C6H15N*C27H29F3NO4PSSi2; C27H26NO4P; hydrogen In dichloromethane under 15001.5 Torr; for 18h; Reagent/catalyst; enantioselective reaction;	n/a
With palladium 10% on activated carbon; hydrogen; potassium carbonate In methanol at 20℃; under 760.051 Torr; for 7h;

methyl 2-hydroxymethylacrylate (15484-46-5) + tert-butylchlorodiphenylsilane (58479-61-1) → methyl 2-(((tert-butyldiphenylsilyl)oxy)methyl)acrylate

Conditions	Yield
With 1H-imidazole In dichloromethane at 0 - 20℃; for 1h;	97%
In N,N-dimethyl-formamide at 0 - 20℃; for 19h;	89%
With 1H-imidazole In N,N-dimethyl-formamide at 0 - 20℃; for 16h;	87%

(5-methyl-pyridin-2-yl)amine (1603-41-4) + methyl 2-hydroxymethylacrylate (15484-46-5) → 3,7-dimethyl-2H-pyrido[1,2-a]pyrimidin-2-one

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol Reflux;	95%
With N-heterocyclic carbene palladium(II) complex supported on fibrous nanosilica In trifluoroacetic acid for 1h; Reflux; Green chemistry; chemoselective reaction;

methyl 2-hydroxymethylacrylate (15484-46-5) + acryloyl chloride (814-68-6) → 2-acryloyloxymethyl-acrylic acid methyl ester

Conditions	Yield
With triethylamine	92%

chloro-trimethyl-silane (75-77-4) + methyl 2-hydroxymethylacrylate (15484-46-5) → methyl 2-trimethylsilyloxymethylacrylate (1158177-66-2)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃;	92%

3-methylpyridin-2-ylamine (1603-40-3) + methyl 2-hydroxymethylacrylate (15484-46-5) → 3,9-dimethyl-2H-pyrido[1,2-a]pyrimidin-2-one

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol Reflux;	92%
With N-heterocyclic carbene palladium(II) complex supported on fibrous nanosilica In trifluoroacetic acid for 1h; Reflux; Green chemistry; chemoselective reaction;

methyl 2-hydroxymethylacrylate (15484-46-5) + tert-butyldimethylsilyl chloride (18162-48-6) → 2-(tert-butyl-dimethyl-silanyloxymethyl)-acrylic acid methyl ester (144828-45-5)

Conditions	Yield
With dmap; TEA In dichloromethane at 0 - 20℃;	91%
With 1H-imidazole In N,N-dimethyl-formamide at 0℃; Inert atmosphere;	82%
With dmap; triethylamine In dichloromethane at 0 - 20℃; Sealed tube; Inert atmosphere;	81%

methyl 2-hydroxymethylacrylate (15484-46-5) + benzylamine (100-46-9) → methyl 2-[(N-benzylamino)methyl]-3-hydroxypropanoate (1023326-56-8)

Conditions	Yield
In methanol at 20℃; for 16h;	91%

methyl 2-hydroxymethylacrylate (15484-46-5) + Tosyl isocyanate (4083-64-1) → C13H15NO6S

Conditions	Yield
In dichloromethane at 0℃;	91%

2-aminopyridine (504-29-0) + methyl 2-hydroxymethylacrylate (15484-46-5) → 3-methyl-2H-pyrido[1,2-a]pyrimidin-2-one (1390649-05-4)

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol for 12h; Reflux;	90%
With N-heterocyclic carbene palladium(II) complex supported on fibrous nanosilica In trifluoroacetic acid for 1h; Solvent; Reagent/catalyst; Reflux; Green chemistry; chemoselective reaction;

methyl 2-hydroxymethylacrylate (15484-46-5) → methyl 2-(bromomethyl)propenoate (4224-69-5)

Conditions	Yield
With phosphorus tribromide In diethyl ether Inert atmosphere;	89%
With phosphorus tribromide In diethyl ether at 0 - 20℃; for 2h;	87.4%
With phosphorus tribromide In acetonitrile at 20℃; for 4h;	86%

dimethylsulfide (75-18-3) + methyl 2-hydroxymethylacrylate (15484-46-5) → methyl 2-(bromomethyl)propenoate (4224-69-5)

Conditions	Yield
With N-Bromosuccinimide; sodium chloride In diethyl ether; dichloromethane	89%

methyl 2-hydroxymethylacrylate (15484-46-5) + N-benzyloxy-α-methyl-α-bromopropionamide (1303507-75-6) → methyl 2-(((1-((benzyloxy)amino)-2-methyl-1-oxopropan-2-yl)-oxy)methyl)acrylate

Conditions	Yield
With sodium carbonate at 20℃; for 3h; Inert atmosphere;	89%

methyl 2-hydroxymethylacrylate (15484-46-5) → 3-hydroxy-(2S)-methylpropionate (80657-57-4)

Conditions	Yield
With diisopropyl{1-[(S)-3,5-dioxa-4-phospha-cyclohepta(2,1-a;3,4-a')dinaphthalen-4-yl]-3-methyl-2-indolyl}phosphine; bis(norbornadiene)rhodium(l)tetrafluoroborate; hydrogen In dichloromethane at -40℃; under 15001.5 Torr; for 15h; Reactivity; Pressure; Temperature; Concentration; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	87%
With N-methyl-N-{(S)-1-[2-(diphenylphosphino)phenyl]ethyl}-(S)-1,10-bi-2-naphthylphosphoramidite; bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In dichloromethane at 20℃; under 7500.75 Torr; for 24h; optical yield given as %ee;
With BF4(1-)*C8H10Rh(1+)*C17H27NO2P2; hydrogen In dichloromethane at 25℃; under 750.075 Torr; for 1.5h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;

methyl 2-hydroxymethylacrylate (15484-46-5) + diethylazodicarboxylate (1972-28-7) → C11H18N2O6

Conditions	Yield
With triphenylphosphine In dichloromethane at 0 - 20℃; for 0.216667h; Mitsunobu Displacement; Inert atmosphere; Schlenk technique; stereoselective reaction;	87%

methyl 2-hydroxymethylacrylate (15484-46-5) → 2-(hydroxymethyl)acrylic acid (4370-80-3)

Conditions	Yield
With methanol; potassium hydroxide In tetrahydrofuran; water at 20℃; for 24h;	85%

triisopropylsilyl chloride (13154-24-0) + methyl 2-hydroxymethylacrylate (15484-46-5) → methyl 2-(((triisopropylsilyl)oxy)methyl)acrylate (1187192-35-3)

Conditions	Yield
With 1H-imidazole In dichloromethane at 0 - 20℃; for 1h;	85%
With 1H-imidazole; dmap In dichloromethane at 20℃; for 18h; Inert atmosphere;	123.3 mg
With 1H-imidazole In dichloromethane Inert atmosphere;

2-amino-5-iodopyridine (20511-12-0) + methyl 2-hydroxymethylacrylate (15484-46-5) → 7-iodo-3-methyl-2H-pyrido[1,2-a]pyrimidin-2-one

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol Reflux;	85%
With N-heterocyclic carbene palladium(II) complex supported on fibrous nanosilica In trifluoroacetic acid for 1h; Reflux; Green chemistry; chemoselective reaction;

methyl 2-hydroxymethylacrylate (15484-46-5) + 2-chloro-1,1,1-trimethoxyethane (74974-54-2) → dimethyl 2-chloro-4-methylenepentanedioate

Conditions	Yield
With acetic acid In toluene at 130℃; for 24h;	85%

methyl 2-hydroxymethylacrylate (15484-46-5) + Cinnamyl bromide (4392-24-9) → methyl (E)-2-((cinnamyloxy)methyl)acrylate

Conditions	Yield
Stage #1: methyl 2-hydroxymethylacrylate With sodium hydride In tetrahydrofuran at 0 - 20℃; Inert atmosphere; Schlenk technique; Stage #2: Cinnamyl bromide In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique;	84%

methyl 2-hydroxymethylacrylate (15484-46-5) + 3-fluoropyridin-2-amine (21717-95-3) → 9-fluoro-3-methyl-2H-pyrido[1,2-a]pyrimidin-2-one

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol Reflux;	83%

methyl 2-hydroxymethylacrylate (15484-46-5) + 3-bromo-5-methylpyridin-2-amine (17282-00-7) → 9-bromo-3,7-dimethyl-2H-pyrido[1,2-a]pyrimidin-2-one

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol Reflux;	83%

cyclopentadienyl titanium(IV) trichloride (1270-98-0) + methyl 2-hydroxymethylacrylate (15484-46-5) → (2-carbethoxyprop-2-enoxy)bischloro-η5-cyclopentadienyl titanium(IV) (153091-07-7)

Conditions	Yield
With triethylamine In benzene (Ar); stirring (2 h); evapn. (vac.), sublimation (80°C, 0.01 Torr), recrystn. (toluene/hexanes); elem. anal.;	82%

methyl 2-hydroxymethylacrylate (15484-46-5) + 4-nitro-benzoyl chloride (122-04-3) → 4-nitrobenzoic acid 2-methoxycarbonyl-allyl ester (1107635-38-0)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; for 0.75h;	81%

methyl 2-hydroxymethylacrylate (15484-46-5) + (E)-3,5-hexadienoic acid (32775-95-4) → (E)-Hexa-3,5-dienoic acid 2-methoxycarbonyl-allyl ester (81095-98-9)

Conditions	Yield
With pyridine; dicyclohexyl-carbodiimide In diethyl ether at 0℃; for 12h;	78%

Upstream product

• 67-56-1 methanol 
• 107-19-7 propargyl alcohol 
• 201230-82-2 carbon monoxide 
• 50-00-0 formaldehyd 
• 1779-58-4 (methyloxycarbonylmethyl)triphenylphosphonium bromide 
• 5927-18-4 trimethyl phosphonoacetate 
• 140-88-5 ethyl acrylate 
• 280-57-9 1,4-diaza-bicyclo[2.2.2]octane 
• 292638-85-8 acrylic acid methyl ester 
• 10029-04-6 ethyl 2-(hydroxymethyl)acrylate 
• 13463-39-3 tetracarbonyl nickel 
• 89533-83-5 2-acetoxymethyl-acrylic acid 

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HYDROXYL GROUP-CONTAINING VINYL COMPOUND PRODUCTION PROCESS

PROBLEM TO BE SOLVED: To provide a hydroxyl group-containing vinyl compound production process in which a hydroxyl group-containing vinyl compound, in which the content of ether dimer of hydroxyl group-containing vinyl compound having high skin irritancy is sufficiently suppressed, can be produced at a lower cost than before. SOLUTION: Provided is a hydroxyl group-containing vinyl compound production process. The production process comprises a step of reacting an acrylic acid ester and an aldehyde compound in the presence of a tertiary amine compound, and a step of removing the acrylic acid ester from the reaction liquid after the reaction step, and is characterized in that the content of the ether dimer of the hydroxyl group-containing vinyl compound in the reaction liquid after the acrylic acid ester removing step is 9.0 mass% or less with respect to 100 mass% of the hydroxyl group-containing vinyl compound. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT