3395-91-3

Basic information

• Product Name: Methyl 3-bromopropionate
• Synonyms: 3-bromopropanoicacidmethylester;3-bromo-propanoicacimethylester;3-bromo-propionicacimethylester;Methyl 3-bromopropanoate;methyl3-bromopropanoate;Propionic acid, 3-bromo-, methyl ester;BETA-BROMOPROPIONIC ACID METHYL ESTER;METHYL 3-BROMOPROPIONATE
• CAS NO: 3395-91-3
• Molecular Formula: C₄H₇BrO₂
• Molecular Weight: 167
• EINECS: 222-247-5
• Product Categories: Organics;C2 to C5;Carbonyl Compounds;Esters;Building Blocks;C2 to C5;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
• Mol File: 3395-91-3.mol
• Article Data: 12

Chemical Properties

• Melting Point: 75°C
• Boiling Point: 64-66 °C18 mm Hg(lit.)
• Flash Point: 167 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 1.53 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.78mmHg at 25°C
• Refractive Index: n20/D 1.458(lit.)
• Storage Temp.: Store at R.T.
• Water Solubility: Immiscible
• BRN: 1742949
• CAS DataBase Reference: Methyl 3-bromopropionate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 3-bromopropionate(3395-91-3)
• EPA Substance Registry System: Methyl 3-bromopropionate(3395-91-3)

Safety Data

• Hazard Codes: Xn
• Statements: 22-36/37/38
• Safety Statements: 26-37/39-24/25
• WGK Germany: 3
• RTECS: UA2451790
• TSCA: Yes
• Hazardous Substances Data: 3395-91-3(Hazardous Substances Data)

Usage

Chemical Properties

Very slightly yellow liquid

Uses

Methyl 3-bromopropionate was used in the synthesis of spiroanellated γ-lactones, pinacols and unprecedented 3-(1-hydroxycycloalkyl)-l-oxaspiro[n,m]alkan-2-ones.

InChI:InChI=1/C4H7BrO2/c1-7-4(6)2-3-5/h2-3H2,1H3

Synthetic route

acrylic acid methyl ester (292638-85-8) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With boron tribromide; ethylene glycol In dichloromethane at 0 - 20℃; for 24h; Concentration; Inert atmosphere;	96%
With diethyl ether; hydrogen bromide anfangs unter Eiskuehlung, dann bei Raumtemperatur;
With hydrogen bromide
With hydrogen bromide In chloroform-d1

Acetyl bromide (506-96-7) + acrylic acid methyl ester (292638-85-8) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With hydroquinone In methanol at 20 - 50℃; for 2h;	96%

propanoic acid methyl ester (554-12-1) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 6h;	88%
With N-Bromosuccinimide; dibenzoyl peroxide

3-Bromopropionic acid (590-92-1) + methanol (67-56-1) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With thionyl chloride at 20℃; for 12h;	81%
In dichloromethane for 18h; Reflux;	81%
With sulfuric acid for 5h; Heating;	70%

methanol (67-56-1) + Tetracarbonyleisenkomplexe des Ethylens → Methyl 3-bromopropionate (3395-91-3) + methyl 3-methoxypropionate (3852-09-3) + ethylene dibromide (106-93-4) + 2-Bromoethyl methyl ether (6482-24-2)

Conditions	Yield
With bromine at -80℃; temperature up to 30 deg C;	A 67% B n/a C n/a D n/a

methanol (67-56-1) + β-Propiolactone (57-57-8) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
Stage #1: β-Propiolactone With hydrogen bromide; acetic acid at 20℃; for 20h; Stage #2: methanol at 20℃; for 15h;	56%

ethanol (64-17-5) → Ethyl 3-bromopropionate (539-74-2) + Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With Acetyl bromide; hydroquinone; ethyl acrylate at 20 - 50℃; for 2h; Overall yield = 88.5 g;	A n/a B 53%

methanol (67-56-1) + ethyl acrylate (140-88-5) → Ethyl 3-bromopropionate (539-74-2) + Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With Acetyl bromide; hydroquinone at 20 - 55℃; for 2h; Overall yield = 92.3 g;	A 51% B n/a

1-bromovinylbenzene (98-81-7) + acrylic acid (79-10-7) → Methyl 3-bromopropionate (3395-91-3) + (+/-)-1,2-dihydro-[1]naphthoic acid (16827-42-2)

Conditions	Yield
With toluene

methyl hydrogen succinate (3878-55-5) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
(i) TlOEt, (ii) Br2; Multistep reaction;

methyl β-diazopropionate (14213-56-0) → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With hydrogen bromide In diethyl ether

methanol (67-56-1) + 3-bromo-N-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)propanamide → Methyl 3-bromopropionate (3395-91-3)

Conditions	Yield
With boron trifluoride diethyl etherate at 100℃; for 20h; Sealed tube;	85 %Spectr.

2-Methyl-1H-benzimidazole (615-15-6) + Methyl 3-bromopropionate (3395-91-3) → methyl-3-(2-methyl-1H-1,3-benzodiazol-1-yl)propanoate (138942-42-4)

Conditions	Yield
With sodium hydride In tetrahydrofuran Ambient temperature;	100%
With potassium carbonate In N,N-dimethyl-formamide	96%
With potassium carbonate In N,N-dimethyl-formamide at 85℃; for 16h;	96%
With potassium carbonate In N,N-dimethyl-formamide	96%

Methyl 3-bromopropionate (3395-91-3) → azido-b-alanine methyl ester (23605-39-2)

Conditions	Yield
With sodium azide In dimethyl sulfoxide at 45℃; for 24h;	100%
With sodium azide In water; acetone at 60℃; for 4h; Inert atmosphere;	98%
With sodium azide In dimethyl sulfoxide Ambient temperature;	94%

4-nitro-1H-pyrazole (2075-46-9) + Methyl 3-bromopropionate (3395-91-3) → 3-(4-nitro-pyrazol-1-yl)-propionic acid

Conditions	Yield
Stage #1: 4-nitro-1H-pyrazole; Methyl 3-bromopropionate With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 3h; Stage #2: With water; lithium hydroxide In methanol at 20℃; for 0.5h;	100%

Methyl 3-bromopropionate (3395-91-3) + 5-methoxy-1-methyl-1H-benzo[d]imidazole-2-thiol → C13H16N2O3S

Conditions	Yield
In methanol at 20 - 82℃; for 24h;	100%

Methyl 3-bromopropionate (3395-91-3) + Dimethyl(phenyl)phosphine (672-66-2) → (3-methoxy-3-oxopropyl)dimethyl(phenyl)phosphonium bromide

Conditions	Yield
In acetonitrile at 20℃;	99%

2-Hydroxybenzophenone (117-99-7) + Methyl 3-bromopropionate (3395-91-3) → (3-phenylbenzofuran-2-yl)acetic acid methyl ester (60312-26-7)

Conditions	Yield
With potassium carbonate at 80℃;	99%

Methyl 3-bromopropionate (3395-91-3) + [NMe4][1-(MeS)-7-(Me2S)B12H10] → 1-(MeS(CH2)2C(O)OMe)-7-(Me2S)B12H10 (414868-01-2)

Conditions	Yield
In acetonitrile to soln. (Me4N)(B12H10(SMe2)SMe) in MeCN excess alkyl halide was added and stirred overnight; volatiles were removed in vacuo, residue was treated with water and CH2Cl2, organic phase was dried over MgSO4, solvent was removed;	97%

Methyl 3-bromopropionate (3395-91-3) + phenylacetylene (536-74-3) → 3-(4-phenyl-[1,2,3]triazol-1-yl)-propionic acid methyl ester (68979-66-8)

Conditions	Yield
With sodium azide; sodium hydroxide In water at 55℃; for 3h; Huisgen Cycloaddition; Green chemistry; regioselective reaction;	97%
With sodium azide; sodium L-ascorbate In water at 50℃; for 2h; Huisgen Cycloaddition; Green chemistry;	96%
With sodium azide; sodium L-ascorbate In water; tert-butyl alcohol at 55℃; for 2.5h; Huisgen Cycloaddition; Green chemistry; regioselective reaction;	95%

Methyl 3-bromopropionate (3395-91-3) + N-(2-aminomethyl)-5-isoquinolinesulfonamide (84468-17-7) → methyl N-(2-isoquinoline-5-sulfonamidoethyl)-3-amino-propionate (129786-37-4)

Conditions	Yield
With triethylamine In methanol for 4h; Heating;	95%

Methyl 3-bromopropionate (3395-91-3) → methyl 3-iodopropanoate (5029-66-3)

Conditions	Yield
With sodium iodide In acetone at 20℃;	95%
With sodium iodide In acetone 1.) 2 h, 2.) 50 deg C, 45 min; Yield given;
With sodium iodide In acetone

Methyl 3-bromopropionate (3395-91-3) + benzyl-methyl-amine (103-67-3) → methyl 3-propanoate (17946-01-9)

Conditions	Yield
With sodium carbonate In acetonitrile at 70℃; for 70h;	95%
With sodium carbonate In acetonitrile at 70℃; for 70h;	95%
With sodium carbonate In acetonitrile at 70℃; for 24h; Inert atmosphere;	92%
With sodium carbonate In acetonitrile at 70℃; for 24h;	92%

Methyl 3-bromopropionate (3395-91-3) + (R)-tetrahydropapaverine N-acetyl-L-leucine salt + oxalic acid (144-62-7) → (1R)-1-[(3,4-dimethoxyphenyl)-methyl]-1,2,3,4-tetrahydro-6,7-dimethoxy-2-methoxycarbonylethyl-isoquinoline oxalate (1075726-76-9)

Conditions	Yield
Stage #1: Methyl 3-bromopropionate; (R)-tetrahydropapaverine N-acetyl-L-leucine salt With sodium carbonate In water; toluene; acetonitrile at 55 - 80℃; for 24h; pH=9; Stage #2: oxalic acid In acetone Temperature; Reagent/catalyst; pH-value;	95%

Methyl 3-bromopropionate (3395-91-3) + piperidine-4-carboxylic acid [2-(4-methoxy-phenyl)-ethyl]-amide (1016755-45-5) → 3-{4-[2-(4-methoxy-phenyl)-ethylcarbamoyl]-piperidin-1-yl}-propionic acid methyl ester

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 50℃; for 48h;	94%

Methyl 3-bromopropionate (3395-91-3) + triphenylphosphine (603-35-0) → C22H22O2P(1+)*Br(1-) (937233-06-2)

Conditions	Yield
In toluene for 12h; Reflux;	94%

Methyl 3-bromopropionate (3395-91-3) + 3,3-diphenylazetidine hydrogen oxalate → C19H21NO2*C2H2O4

Conditions	Yield
With sodium hydrogencarbonate In N,N-dimethyl-formamide at 110℃; for 16h; Inert atmosphere;	94%

Methyl 3-bromopropionate (3395-91-3) + ethylmagnesium bromide (925-90-6) → 1-(2-bromoethyl)cyclopropan-1-ol (128312-82-3)

Conditions	Yield
With titanium(IV) isopropylate In tetrahydrofuran; diethyl ether at 20℃; for 4h;	92%
With titanium(IV) isopropylate In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere;	12%
With titanium(IV) isopropylate In diethyl ether at 18 - 20℃; for 0.166667h;
Stage #1: Methyl 3-bromopropionate; ethylmagnesium bromide With titanium(IV) isopropylate In diethyl ether Stage #2: With sulfuric acid; water In diethyl ether at 0℃;

quinoline (91-22-5) + Methyl 3-bromopropionate (3395-91-3) → 1-(2-carbmethoxyethyl)-quinolinium hexafluorophosphate

Conditions	Yield
Stage #1: quinoline; Methyl 3-bromopropionate In ethanol for 4h; Heating; Stage #2: With ammonium hexafluorophosphate In water at 20℃;	92%

6-bromo-3,4-dihydroisoquinolin-1(2H)-one (147497-32-3) + Methyl 3-bromopropionate (3395-91-3) → 3-(6-bromo-1-oxo-3,4-dihydro-1H-isoquinolin-2-yl)propionic acid methyl ester

Conditions	Yield
Stage #1: 6-bromo-3,4-dihydroisoquinolin-1(2H)-one With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.5h; Stage #2: Methyl 3-bromopropionate In tetrahydrofuran; mineral oil for 2h; Reflux;	92%

Methyl 3-bromopropionate (3395-91-3) → C4H5BrN2O2

Conditions	Yield
With C8H8N4O4S; triethylamine In 1,2-dichloro-ethane at 0 - 20℃; for 1h;	92%

6-chloro-4(1H)-cinnoline (18514-88-0) + Methyl 3-bromopropionate (3395-91-3) → 3-(6-Chloro-4-oxo-4H-cinnolin-1-yl)-propionic acid methyl ester (1027195-94-3)

Conditions	Yield
With potassium carbonate In acetone for 5h; Ambient temperature;	91.2%

Methyl 3-bromopropionate (3395-91-3) + 3-Bromo-6-methyl-1H-cinnolin-4-one → 3-(3-Bromo-6-methyl-4-oxo-4H-cinnolin-1-yl)-propionic acid methyl ester

Conditions	Yield
With potassium carbonate In acetonitrile for 10h; Heating;	91.2%

Methyl 3-bromopropionate (3395-91-3) → 1,1-dideuterio-3-bromopropanol (81344-31-2)

Conditions	Yield
With aluminum (III) chloride; lithium aluminium deuteride In diethyl ether at -20℃; for 1h; Inert atmosphere;	91%
With aluminium trichloride; lithium aluminium deuteride	2.89%

Methyl 3-bromopropionate (3395-91-3) + 3-chloro-aniline (108-42-9) → methyl N-(3-chlorophenyl)-β-alaninate (42313-47-3)

Conditions	Yield
With sodium carbonate for 6h; Heating;	91%

Methyl 3-bromopropionate (3395-91-3) + 4-fluoroaniline (371-40-4) → 3-bromo-N-(4-fluorophenyl)propionamide (135154-75-5)

Conditions	Yield
Stage #1: 4-fluoroaniline With trimethylaluminum In tetrahydrofuran; hexane at -78 - 20℃; for 0.333333h; Stage #2: Methyl 3-bromopropionate In tetrahydrofuran; hexane for 2h; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane at 0℃;	91%
Stage #1: 4-fluoroaniline With trimethylaluminum In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #2: Methyl 3-bromopropionate In tetrahydrofuran; hexane at 20℃; for 3h;

5,6-dichloro-2-methylbenzimidazole (6478-79-1) + Methyl 3-bromopropionate (3395-91-3) → methyl 3-(5,6-dichloro-2-methyl-1H-benzimidazol-1-yl)propanoate (1449030-60-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 85℃; for 16h;	91%

Methyl 3-bromopropionate (3395-91-3) + 1H-4(5)-nitroimidazole (3034-38-6) → 3-(4-nitro-imidazol-1-yl)-propionic acid methyl ester (328056-86-6)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide; potassium carbonate In acetonitrile at 80℃; for 0.5h;	90%

6-methoxy-3-(4-methoxy-phenylsulfonyl)-1H-indole (889129-61-7) + Methyl 3-bromopropionate (3395-91-3) → 3-[6-methoxy-3-(4-methoxy-benzenesulfonyl)-indol-1-yl]-propionic acid methyl ester

Conditions	Yield
Stage #1: 6-methoxy-3-(4-methoxy-phenylsulfonyl)-1H-indole With potassium hydroxide; tetra(n-butyl)ammonium hydrogensulfate In dichloromethane; water at 20℃; for 0.0833333h; Stage #2: Methyl 3-bromopropionate In dichloromethane; water at 20℃; for 16h;	90%

Methyl 3-bromopropionate (3395-91-3) + 1-t-Butoxycarbonylpiperazine (57260-71-6) → 4-(2-methoxycarbonylethyl)-piperazine-1-carboxylic acid tert-butyl ester (656803-51-9)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃;	90%
With N-ethyl-N,N-diisopropylamine In acetonitrile at 50℃; for 18h; Inert atmosphere;	85%
With caesium carbonate In N,N-dimethyl-formamide at 20℃;	74%
With triethylamine In tetrahydrofuran at 20℃; for 18h;

Upstream product

• 98-81-7 1-bromovinylbenzene 
• 79-10-7 acrylic acid 
• 506-96-7 Acetyl bromide 
• 292638-85-8 acrylic acid methyl ester 
• 67-56-1 methanol 
• 140-88-5 ethyl acrylate 
• 64-17-5 ethanol 
• 57-57-8 β-Propiolactone 
• 14213-56-0 methyl β-diazopropionate 
• 3878-55-5 methyl hydrogen succinate 
• 590-92-1 3-Bromopropionic acid 
• 554-12-1 propanoic acid methyl ester 

Downstream Products

• 1003580-17-3 6t-phenyl-hexa-3ξ,5-dienoic acid 
• 13532-18-8 methyl 3-(methylthio)propionate 
• 105-71-5 3-methyl[(3-methoxy-3-oxopropyl)methylamino]propanoate 
• 20497-95-4 methyl 3-nitropropionate 
• 75844-17-6 3-(1-methoxycarbonyl-2-oxo-cyclohexyl)-propionic acid methyl ester 
• 46917-61-7 6-(2-methoxy-ethyl)-N²-phenyl-[1,3,5]triazine-2,4-diyldiamine 
• 10312-37-5 methyl 4-nitropentanoate 
• 16507-02-1 methyl 4-methyl-4-nitropentanoate 
• 38648-79-2 4-(2-methoxycarbonyl-ethyl)-5,5-dimethyl-2-phenyl-4,5-dihydro-thiazole-4-carboxylic acid methyl ester 
• 77549-12-3 (R)-2-Acetylamino-3-(2-methoxycarbonyl-ethylsulfanyl)-propionic acid 
• 699-61-6 1-oxaspiro[4.5]decan-2-one 
• 2888-11-1 1,1'-bicyclohexane-1,1'-diol 
• 137170-79-7 3-(1-hydroxycyclohexyl)-1-oxaspiro<4.5>decan-2-one 
• 170646-73-8 3-(4-Oxo-4H-cinnolin-1-yl)-propionic acid methyl ester 

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