5437-45-6

Basic information

• Product Name: Benzyl 2-bromoacetate
• Synonyms: bromo-aceticacibenzylester;bromo-aceticaciphenylmethylester;merbac35;TIMTEC-BB SBB006752;BROMOACETIC ACID BENZYL ESTER;BENZYL BROMOACETATE;BENZYL 2-BROMOACETATE;2-BROMO-ACETIC ACID BENZYLESTER
• CAS NO: 5437-45-6
• Molecular Formula: C₉H₉BrO₂
• Molecular Weight: 229.07
• EINECS: 226-611-4
• Product Categories: Pharmaceutical Intermediates;Building Blocks;C8 to C9;Carbonyl Compounds;Chemical Synthesis;Esters;Organic Building Blocks
• Mol File: 5437-45-6.mol
• Article Data: 58

Chemical Properties

• Melting Point: 199-201 °C(Solv: water (7732-18-5))
• Boiling Point: 166-170 °C22 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: Clear colorless to light yellow/Liquid
• Density: 1.446 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.00243mmHg at 25°C
• Refractive Index: n20/D 1.544(lit.)
• Storage Temp.: Store below +30°C.
• Solubility: Chloroform, Methanol
• Water Solubility: Not miscible or difficult to mix in water.
• BRN: 973658
• CAS DataBase Reference: Benzyl 2-bromoacetate(CAS DataBase Reference)
• NIST Chemistry Reference: Benzyl 2-bromoacetate(5437-45-6)
• EPA Substance Registry System: Benzyl 2-bromoacetate(5437-45-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39
• RIDADR: 2810
• WGK Germany: 3
• RTECS: AF5957215
• F: 19
• Hazardous Substances Data: 5437-45-6(Hazardous Substances Data)

Usage

Chemical Properties

Colorless to light yellow liqui

Uses

It is employed in biological research purpose. Benzyl bromoacetate was used in the alkylation of (-)-2,3-O-isopropylidene-D-threitol that afforded lipopeptide, 2-[(4R,5R)-5-({[(9H-fluoren-9-yl)methoxy]carbonylaminomethyl}-2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]acetic acid.

Purification Methods

Dilute the ester with Et2O, wash it with 10% aqueous NaHCO3, H2O, dry (MgSO4) and fractionate it using a Fenske (glass helices packing) column. [Bergmann & Szinai J Chem Soc 1521 1956, Beilstein 6 IV 2265.] LACHRYMATORY.

InChI:InChI=1/C9H9BrO2/c10-6-9(11)12-7-8-4-2-1-3-5-8/h1-5H,6-7H2

Synthetic route

bromoacetic acid (79-08-3) + benzyl alcohol (100-51-6) → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With toluene-4-sulfonic acid In benzene at 120℃; for 24h;	100%
With toluene-4-sulfonic acid In benzene at 120℃; for 24h; Inert atmosphere;	100%
With toluene-4-sulfonic acid In benzene at 120℃; for 24h;	100%

2-Bromoacetyl bromide (598-21-0) + benzyl alcohol (100-51-6) → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With sodium hydrogencarbonate In acetonitrile at 0℃; for 0.916667h; Sealed tube; Inert atmosphere;	98%
With dmap In dichloromethane at 20℃; for 2h; Inert atmosphere;	94%
With 2,6-dimethylpyridine In dichloromethane at 0℃; for 2h;	91%

bromoacetic acid methyl ester (96-32-2) + benzyl alcohol (100-51-6) → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With 1,3-bis(2,4,6-trimethylphenyl)imidazole hydrochloride; potassium tert-butylate In benzene at 80℃; for 10h; Inert atmosphere;	85%

bromoacetic acid (79-08-3) + benzyl alcohol (100-51-6) → dibenzyl ether (103-50-4) + Benzyl bromoacetate (5437-45-6)

Conditions	Yield
In neat (no solvent) at 80℃; for 6h; Inert atmosphere;	A n/a B 82%

benzyl 2-(tributylstannyl)acetate → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With tetrabutylammonium hexanitratocerate(IV); carbon tetrabromide; potassium carbonate In acetonitrile at 0℃; for 2h;	68%

ethyl bromoacetate (105-36-2) + benzyl alcohol (100-51-6) → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With toluene-4-sulfonic acid; toluene unter Entfernen des entstehenden Aethanols;

1-ethoxy-1-cyclopropanol (13837-45-1) + benzyloxycarbonylbromomethylenetriphenylphosphorane (78385-35-0) → benzyl 2-bromocyclopropylideneacetate (78385-37-2) + Benzyl bromoacetate (5437-45-6)

Conditions	Yield
In benzene for 3.5h; Yields of byproduct given;

benzyloxycarbonylbromomethylenetriphenylphosphorane (78385-35-0) → benzyl 2-bromocyclopropylideneacetate (78385-37-2) + Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With 1-ethoxypropanol; benzoic acid In benzene for 3.5h; Yield given;

dibenzyl ether (103-50-4) + 2-Bromoacetyl bromide (598-21-0) → benzyl bromide (100-39-0) + Benzyl bromoacetate (5437-45-6)

Conditions	Yield
at 100℃; for 10h; Product distribution;

benzyl bromo acetate + phenol (108-95-2) → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide

bromoacetic acid (79-08-3) + benzyl alcohol (100-51-6) → Benzyl bromoacetate (5437-45-6)

Conditions	Yield
With sulfuric acid; sodium acetate trihydrate; sodium hydrogencarbonate; toluene-4-sulfonic acid; acetic acid; benzyl alcohol; aluminum nickel In ethanol; cyclohexane; water

pyridine (110-86-1) + Benzyl bromoacetate (5437-45-6) → N-(Benzyloxycarbonylmethyl)pyridinium bromide (136383-19-2)

Conditions	Yield
	100%
In acetone at 60℃; Inert atmosphere;

tert-butyl 2-(benzylamino)acetate (7662-76-2) + Benzyl bromoacetate (5437-45-6) → (Benzyl-benzyloxycarbonylmethyl-amino)-acetic acid tert-butyl ester (185426-26-0)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide 1.) 0 deg C, 30 min, 2.) room temperature, 3 h;	100%

tert-butyl {2-[benzylamino]ethyl}carbamate (174799-52-1) + Benzyl bromoacetate (5437-45-6) → benzyl 2-(benzyl{2-[(tert-butoxycarbonyl)amino]ethyl}amino)acetate

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide 1.) 0 deg C, 30 min, 2.) room temperature, 3 h;	100%
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 0 - 20℃;	90%

N-[N-(tert-Butyloxycarbonyl)-3-aminopropyl]benzylamine (90914-08-2) + Benzyl bromoacetate (5437-45-6) → [Benzyl-(3-tert-butoxycarbonylamino-propyl)-amino]-acetic acid benzyl ester (174799-95-2)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide 1.) 0 deg C, 30 min, 2.) room temperature, 3 h;	100%

N(1)-benzyl-N(4)-(tert-butyloxycarbonyl)-1,4-diaminobutane (90914-09-3) + Benzyl bromoacetate (5437-45-6) → [Benzyl-(4-tert-butoxycarbonylamino-butyl)-amino]-acetic acid benzyl ester (174799-96-3)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide 1.) 0 deg C, 30 min, 2.) room temperature, 3 h;	100%

(6-Benzylamino-hexyl)-carbamic acid tert-butyl ester (174799-53-2) + Benzyl bromoacetate (5437-45-6) → [Benzyl-(6-tert-butoxycarbonylamino-hexyl)-amino]-acetic acid benzyl ester (174799-97-4)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide 1.) 0 deg C, 30 min, 2.) room temperature, 3 h;	100%

(1R,5R)-6-hydroxy-7-oxo-2,6-diazabicyclo[3.2.0]heptane-2-carboxylic acid tert-butyl ester (214412-65-4) + Benzyl bromoacetate (5437-45-6) → (1S,5R)-6-Benzyloxycarbonylmethoxy-7-oxo-2,6-diaza-bicyclo[3.2.0]heptane-2-carboxylic acid tert-butyl ester (214412-66-5)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 0℃; for 1h;	100%

(1R,3S)-1-[(1-adamantyl)methyl]-2-acetyl-1-(2-fluorobenzyl)-3-tert-butyloxycarbonylmethylcarbonyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole + Benzyl bromoacetate (5437-45-6) → 2-[2-acetyl-1-adamantan-1-ylmethyl-9-(2-fluoro-benzyl)-2,3,4,9-tetrahydro-1H-β-carboline-3-carbonyl]-succinic acid 4-benzyl ester 1-tert-butyl ester (303767-15-9)

Conditions	Yield
Stage #1: (1R,3S)-1-[(1-adamantyl)methyl]-2-acetyl-1-(2-fluorobenzyl)-3-tert-butyloxycarbonylmethylcarbonyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole With sodium hydride In tetrahydrofuran at 0℃; for 0.333333h; Metallation; Stage #2: Benzyl bromoacetate In tetrahydrofuran at 20℃; for 2h; Alkylation; Further stages.;	100%

triethyl phosphite (122-52-1) + Benzyl bromoacetate (5437-45-6) → benzyl diethylphosphonoacetate (7396-44-3)

Conditions	Yield
at 150℃;	100%
at 50℃; for 2h;	97%
at 200℃; for 1h;	87%
at 80℃; for 1h;

4-Hydroxyacetophenone (99-93-4) + Benzyl bromoacetate (5437-45-6) → benzyl 2-(4-acetylphenoxy)acetate (851875-31-5)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1.5h; Williamson ether synthesis;	100%
With potassium carbonate In N,N-dimethyl-formamide at 75 - 80℃; for 1.5h;	79.8%

FmocNHNH(CH2)3NHBoc (808733-44-0) + Benzyl bromoacetate (5437-45-6) → Fmoc-aza-β3-Orn(Boc)-Bn (872554-77-3)

Conditions	Yield
With potassium carbonate In toluene for 36h; Reflux;	100%
With potassium carbonate In toluene for 28h; Heating;	60%

tert-butyl {2-[2-(2-aminoethoxy)ethoxy]ethyl}carbamate (153086-78-3) + Benzyl bromoacetate (5437-45-6) → (benzyloxycarbonylmethyl-{2-[2-(2-tert-butoxycarbonylamino-ethoxy)-ethoxy]-ethyl}-amino)-acetic acid benzyl ester (875057-36-6)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran; water at 20℃; for 12h;	100%

4-benzylpyperidine (31252-42-3) + Benzyl bromoacetate (5437-45-6) → (4-benzylpiperidin-1-yl)acetic acid benzyl ester (438634-63-0)

Conditions	Yield
With triethylamine In dichloromethane; ethyl acetate	100%

methyl 2-(m-chlorobenzylideneamino)acetate (866464-53-1) + Benzyl bromoacetate (5437-45-6) → 1,3-dibenzyl-2-methyl 2-(3-chlorobenzylideneamino)propane-1,2,3-tricarboxylate (1175019-83-6)

Conditions	Yield
Stage #1: methyl 2-(m-chlorobenzylideneamino)acetate With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: Benzyl bromoacetate In tetrahydrofuran at -78 - 20℃; Inert atmosphere;	100%

(2R,3R)-dimethyl 2-(7,8-dihydroxy-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-3-(3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yloxy)succinate + Benzyl bromoacetate (5437-45-6) → (2R, 3R)-dimethyl 2-(8-(2-(benzyloxy)-2-oxoethoxy)-7-hydroxy-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-3-(3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yloxy)succinate

Conditions	Yield
Stage #1: (2R,3R)-dimethyl 2-(7,8-dihydroxy-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yloxy)-3-(3,4,5-tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-yloxy)succinate With di(n-butyl)tin oxide In methanol for 2h; Inert atmosphere; Reflux; Stage #2: Benzyl bromoacetate With cesium fluoride In tetrahydrofuran for 1.25h; Inert atmosphere;	100%

5-ethynyluracil (59989-18-3) + Benzyl bromoacetate (5437-45-6) → benzyl 2-[4-(uracil-5-yl)-1H-1,2,3-triazol-1-yl]acetate

Conditions	Yield
Stage #1: Benzyl bromoacetate With copper(l) iodide; sodium azide; sodium L-ascorbate; N,N`-dimethylethylenediamine In ethanol; water at 100℃; for 1h; Stage #2: 5-ethynyluracil In ethanol; water at 100℃; for 0.5h;	100%

2-methyl-4-(trifluoromethyl)-1H-imidazole (33468-67-6) + Benzyl bromoacetate (5437-45-6) → benzyl 2-[2-methyl-4-(trifluoromethyl)imidazol-1-yl]acetate

Conditions	Yield
With potassium carbonate In acetonitrile at 60℃;	100%

3-(2,2,2-trifluoroacetamido)-N-(2-(trifluoromethyl)benzyl)benzamide + Benzyl bromoacetate (5437-45-6) → benzyl 2-(2,2,2-trifluoro-N-(3-((2-(trifluoromethyl)benzyl)carbamoyl)phenyl)acetamido)acetate

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 0 - 20℃;	100%

tert-butyl 4-hydroxy-[1,1'-biphenyl]-3-carboxylate + Benzyl bromoacetate (5437-45-6) → tert-butyl 4-(2-(benzyloxy)-2-oxoethoxy)-[1,1'-biphenyl]-3-carboxylate

Conditions	Yield
Stage #1: tert-butyl 4-hydroxy-[1,1'-biphenyl]-3-carboxylate With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.166667h; Stage #2: Benzyl bromoacetate In N,N-dimethyl-formamide at 45℃; for 2h; Williamson Ether Synthesis;	100%

3-mercaptopropionic acid (107-96-0) + Benzyl bromoacetate (5437-45-6) → C12H14O4S

Conditions	Yield
Stage #1: 3-mercaptopropionic acid With triethylamine In dichloromethane at 20℃; for 0.166667h; Stage #2: Benzyl bromoacetate In dichloromethane at -20 - 20℃; for 24h;	100%

2-bromo-3-fluorophenol (443-81-2) + Benzyl bromoacetate (5437-45-6) → benzyl 2-(2-bromo-3-fluorophenoxy)acetate

Conditions	Yield
With potassium phosphate In acetonitrile at 20℃; for 16h; Inert atmosphere;	99.5%

6-Benzylamino-hexanoic acid tert-butyl ester (185426-12-4) + Benzyl bromoacetate (5437-45-6) → 6-(Benzyl-benzyloxycarbonylmethyl-amino)-hexanoic acid tert-butyl ester (185426-28-2)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide 1.) 0 deg C, 30 min, 2.) room temperature, 3 h;	99.1%

methylhydrazine (60-34-4) + Benzyl bromoacetate (5437-45-6) → benzyl 2-(1-methylhydrazinyl)acetate (55501-33-2)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; for 2h;	99%
With triethylamine In dichloromethane 1.) 0 deg C, 0.5 h, 2.) r.t., 4 h;	98%

Benzyl bromoacetate (5437-45-6) → Benzyl acetate (140-11-4)

Conditions	Yield
With indium; sodium dodecyl-sulfate at 60℃; for 0.5h;	99%
With borohydride exchange resin; nickel diacetate In methanol for 1h; Ambient temperature;	98%
With DMBI In tetrahydrofuran for 1h; Heating;	94%

2-[6-[bis[(1,1-dimethylethoxy)carbonyl]amino]-1,4-dihydro-4-oxo-2-pyridinyl]-1,3-bis(1,1-dimethylethyl)ester (350697-62-0) + Benzyl bromoacetate (5437-45-6) → Benzyl 2-{[2,6-bis(bis(N-tert-butoxycarbonyl)amino)]-4-pyridyloxy} acetate (350697-63-1)

Conditions	Yield
With tetrabutylammomium bromide; potassium carbonate In dimethyl sulfoxide at 20℃; for 18h;	99%

oct-1-ene (111-66-0) + Benzyl bromoacetate (5437-45-6) → benzyl 4-bromodecanoate

Conditions	Yield
With air; triethyl borane In ethanol; water at 25℃; for 1.5h;	99%
With air; triethyl borane; 1-ethyl-3-methylimidazolium tetrafluoroborate at 25℃; for 6h;	86%

3-((S)-3,5-Dioxo-1,4-diaza-spiro[5.5]undec-2-yl)-propionic acid methyl ester (852060-08-3) + Benzyl bromoacetate (5437-45-6) → 3-((S)-4-Benzyloxycarbonylmethyl-3,5-dioxo-1,4-diaza-spiro[5.5]undec-2-yl)-propionic acid methyl ester (1054660-71-7)

Conditions	Yield
With caesium carbonate In acetonitrile at 50℃; for 2h;	99%

5-(((tert-butoxycarbonyl)amino)methyl)-6-isobutyl-2-methyl-4-(4-methylphenyl)nicotinic acid (851577-43-0) + Benzyl bromoacetate (5437-45-6) → 2-(benzyloxy)-2-oxoethyl 5-{[(tert-butoxycarbonyl)amino]methyl}-6-isobutyl-2-methyl-4-(4-methylphenyl)nicotinate (851578-20-6)

Conditions	Yield
With potassium carbonate In DMF (N,N-dimethyl-formamide) at 20℃; for 0.5h;	99%

tris(tert-butyl) 2,2',2''-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetate hydrobromide + Benzyl bromoacetate (5437-45-6) → phenylmethyl 2-(1,4,7,10-Tetraaza-4,7,10-tris(((tert-butyl)oxycarbonyl)methyl)cyclododecyl)-acetate (192635-89-5)

Conditions	Yield
With sodium hydrogencarbonate In acetonitrile at 100℃; for 30h;	99%
With sodium hydrogencarbonate In acetonitrile at 100℃; for 30h;	91%
With potassium carbonate In acetonitrile for 24h; Reflux; Inert atmosphere;	90%
Stage #1: tris(tert-butyl) 2,2',2''-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetate hydrobromide With potassium carbonate In acetonitrile for 0.5h; Stage #2: Benzyl bromoacetate In acetonitrile at 50 - 60℃;

Upstream product

• 79-08-3 bromoacetic acid 
• 100-51-6 benzyl alcohol 
• 105-36-2 ethyl bromoacetate 
• 108-95-2 phenol 
• 96-32-2 bromoacetic acid methyl ester 
• 598-21-0 2-Bromoacetyl bromide 
• 103-50-4 dibenzyl ether 
• 78385-35-0 benzyloxycarbonylbromomethylenetriphenylphosphorane 
• 13837-45-1 1-ethoxy-1-cyclopropanol 

Downstream Products

• 53342-23-7 benzyl morpholino-acetate 
• 136383-19-2 N-(Benzyloxycarbonylmethyl)pyridinium bromide 
• 143023-95-4 benzyl 2-(1'-aza-2'-oxocyclopentyl)ethanoate 
• 80056-42-4 N-benzyloxycarbonylmethylene-2-pyridone 
• 142982-11-4 benzyl 2-<(3-hydroxypropyl)amino>acetate 
• 134807-23-1 Benzyl imidazol-1-ylacetate 
• 152961-69-8 N-[3,5-bis(decyloxy)phenyl]-N-[2-oxo-2-(phenylmethoxy)ethyl]glycine phenylmethyl ester 
• 158387-49-6 <3-<<(benzyloxy)(4-phenylbutyl)phosphinoyl>oxy>-2-oxo-3,4,5,7-tetrahydrocycloheptazepin-1-yl>acetic acid benzyl ester 
• 1027428-18-7 (3-{Benzyloxy-[4-(3-methyl-2-pyridin-3-yl-indol-1-yl)-butyl]-phosphinoyloxy}-2-oxo-2,3,4,5-tetrahydro-benzo[b]azepin-1-yl)-acetic acid benzyl ester 
• 65940-30-9 N-cyclohexylglycine benzyl ester 
• 65940-28-5 N-cyclohexanemethylglycine benzyl ester 
• 126100-77-4 3-O-benzyloxycarbonylmethyl-5,6-O-isopropylidene-L-ascorbic acid 
• 192058-18-7 (Benzyloxycarbonylmethyl-{15-[(bis-benzyloxycarbonylmethyl-amino)-methyl]-1,4,7,10,13-pentaoxa-cyclohexadec-15-ylmethyl}-amino)-acetic acid benzyl ester 

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