98475-07-1

Basic information

• Product Name: Methyl 2-bromomethyl-3-nitrobenzoate
• Synonyms: 2-Bromomethyl-3-NitrobenzoicAcidMethylEster;Methyl 2-bromomethyl-3-nitrobenzoate;Methyl 2-bromomethyl;2-BroMoMethyl-3-nitrobenzoate Methyl ester;Benzoic acid, 2-(broMoMethyl)-3-nitro-, Methyl ester;2-Bromomethyl-3-nitro-benzoic acid;Methyl 2- bromomethyl-3-nitrobezoate;Lenalidomide Impurity 5
• CAS NO: 98475-07-1
• Molecular Formula: C₉H₈BrNO₄
• Molecular Weight: 274.07
• EINECS: 1312995-182-4
• Product Categories: Aromatics;Miscellaneous Reagents
• Mol File: 98475-07-1.mol
• Article Data: 64

Chemical Properties

• Melting Point: 72-74°
• Boiling Point: 370.9 °C at 760 mmHg
• Flash Point: 178.1 °C
• Appearance: /Solid
• Density: 1.624 g/cm³
• Vapor Pressure: 1.07E-05mmHg at 25°C
• Refractive Index: 1.593
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: soluble in Methanol
• CAS DataBase Reference: Methyl 2-bromomethyl-3-nitrobenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 2-bromomethyl-3-nitrobenzoate(98475-07-1)
• EPA Substance Registry System: Methyl 2-bromomethyl-3-nitrobenzoate(98475-07-1)

Safety Data

• RIDADR: UN 3261 8/PG III
• HazardClass: IRRITANT
• PackingGroup: III
• Hazardous Substances Data: 98475-07-1(Hazardous Substances Data)

Usage

Chemical Properties

Pale Yellow Solid

InChI:InChI=1/C9H8BrNO4/c1-15-9(12)6-3-2-4-8(11(13)14)7(6)5-10/h2-4H,5H2,1H3

Synthetic route

2-methyl-3-nitro-benzoic acid methyl ester (59382-59-1) → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane Reflux;	100%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In dichloromethane for 16h; Heating;	98%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In acetic acid methyl ester at 57℃; for 18h;	98%

N-bromo-succinimide (NBS) + methyl 2-methyl-4-nitrobenzoate (62621-09-4) → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
With azobisisobutyronitrile In tetrachloromethane; hexane; dichloromethane	98%

diethyl ether (60-29-7) + 2-methyl-3-nitro-benzoic acid methyl ester (59382-59-1) → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane	88.3%

3-nitro-2-[(triphenyl-λ5-phosphanylidene)-methyl]-benzoic acid methyl ester → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: CH2Cl2 2: benzoyl peroxide; bromine / CCl4 / 46 h / Irradiation; heating View Scheme

N-bromosuccinamide + 2-methyl-3-nitro-benzoic acid methyl ester (59382-59-1) + dibenzoyl peroxide (94-36-0) → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
In tetrachloromethane; ethyl acetate

n-Butyl chloride (109-69-3) + 2-methyl-3-nitro-benzoic acid methyl ester (59382-59-1) → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane; cyclohexane

2-methyl-3-nitrobenzic acid (1975-50-4) → 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: thionyl chloride / 5 h / Reflux 2: N-Bromosuccinimide; dibenzoyl peroxide / tetrachloromethane / Reflux View Scheme
Multi-step reaction with 2 steps 1.1: thionyl chloride / dichloromethane / Reflux 1.2: Reflux 2.1: bromine / tetrachloromethane / 20 °C View Scheme
Multi-step reaction with 2 steps 1: bis(trichloromethyl) carbonate / N,N-dimethyl-formamide / 6 h / Reflux 2: N-Bromosuccinimide; dibenzoyl peroxide / 8 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: sulfuric acid / 24 h / Inert atmosphere; Reflux 2: N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) / benzene / 24 h / Inert atmosphere; Reflux View Scheme

methylamine (74-89-5) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-methyl-4-nitroisoindolin-1-one (682757-52-4)

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 18h; Inert atmosphere;	100%
In tetrahydrofuran; water at 20 - 60℃; for 8h;	91.9%
In methanol at 20℃; for 3h;	50%

rac-α-aminoglutarimide hydrochloride (24666-56-6) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 3-(4-nitro-1-oxoisoindolin-2-yl)piperidine-2,6-dione (827026-45-9)

Conditions	Yield
Stage #1: rac-α-aminoglutarimide hydrochloride With triethylamine In dimethyl sulfoxide for 0.166667h; Inert atmosphere; Stage #2: 2-bromomethyl-3-nitro-benzoic acid methyl ester In dimethyl sulfoxide at 50 - 55℃; for 12.3333h; Inert atmosphere;	99.73%
With sodium carbonate at 100℃; for 0.75h; Reagent/catalyst; Temperature; Inert atmosphere;	98.5%
With sodium carbonate In acetonitrile at 70℃; for 8h; Solvent; Reagent/catalyst; Temperature;	98.8%

triphenylphosphine (603-35-0) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → (2-carbomethoxy-6-nitrobenzyl)triphenylphosphonium bromide

Conditions	Yield
In chloroform for 1h; Heating;	99%
In chloroform for 1.5h; Reflux;

4-methoxy-benzylamine (2393-23-9) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(4-methoxybenzyl)-4-nitroisoindolin-1-one

Conditions	Yield
In tetrahydrofuran at 50℃; for 24h; Inert atmosphere;	99%

propylamine (107-10-8) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 4-nitro-2-propyl-2,3-dihydroisoindol-1-one

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5h; Inert atmosphere;	97%

2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 4-nitro-2,3-dihydro-1H-isoindol-1-one (366452-97-3)

Conditions	Yield
With ammonium hydroxide at 90℃; for 2h;	96.04%
With ammonia In methanol at 20℃; for 2.5h;	90%
With ammonia In methanol at 20℃; for 2h;	81%

aniline (62-53-3) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 4-nitro-2-phenylisoindolin-1-one

Conditions	Yield
at 40℃; for 0.0833333h;	96.03%

2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) + (+/-)-α-aminoglutarimide (2353-44-8) → 3-(4-nitro-1-oxoisoindolin-2-yl)piperidine-2,6-dione (827026-45-9)

Conditions	Yield
In N,N-dimethyl-formamide for 3h; Reflux;	96%
Stage #1: 2-bromomethyl-3-nitro-benzoic acid methyl ester; (+/-)-α-aminoglutarimide With sodium carbonate In acetonitrile at 5℃; Inert atmosphere; Reflux; Large scale; Stage #2: With hydrogenchloride In water at 20 - 62℃; for 4h; pH=< 6; Large scale;	79.5%
With triethylamine In N,N-dimethyl-formamide at 25 - 100℃; for 7h; Inert atmosphere;
With potassium hydrogencarbonate In acetonitrile Reflux;
With triethylamine In N,N-dimethyl-formamide at 75℃; for 20h;

benzylamine (100-46-9) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-benzyl-4-nitro-2,3-dihydroisoindol-1-one (1630974-73-0)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5h; Inert atmosphere;	95%

1,3-dihydro-1-(1-methylethenyl)-2H-benzimidazol-2-one (52099-72-6) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(3-isopropenyl-2-oxo-2,3-dihydro-benzoimidazol-1-ylmethyl)-3-nitro-benzoic acid methyl ester (1090902-91-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20 - 80℃; for 2h;	94%

p-toluidine (106-49-0) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(p-tolyl)-4-nitro-2,3-dihydroisoindol-1-one (1630974-71-8)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5h; Inert atmosphere;	94%

2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-[[(Amino)(imino)methyl]thiomethyl]-3-nitrobenzoic acid, methyl ester, hydrobromide

Conditions	Yield
With thiourea In methanol; ethyl acetate	93%
With thiourea In methanol

(+)-9-amino-5-(4-methoxybenzyl)-2-oxa-5-azaspiro[3.5]nonan-6-one + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → (+)-5-(4-methoxybenzyl)-9-(4-nitro-1-oxoisoindolin-2-yl)-2-oxa-5-azaspiro[3.5]nonan-6-one

Conditions	Yield
With triethylamine In N,N-dimethyl-formamide at 75℃; for 20h; Inert atmosphere;	93%

(-)-9-amino-5-(4-methoxybenzyl)-2-oxa-5-azaspiro[3.5]nonan-6-one + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → (-)-5-(4-methoxybenzyl)-9-(4-nitro-1-oxoisoindolin-2-yl)-2-oxa-5-azaspiro[3.5]nonan-6-one

Conditions	Yield
With triethylamine In N,N-dimethyl-formamide at 75℃; for 20h; Inert atmosphere;	93%

(S)-methyl 4,5-diamino-5-oxopentanoate hydrochloride + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → (S)-methyl 5-amino-4-(4-nitro-1-oxoisoindolin-2-yl)-5-oxopentanoate

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 22℃; for 17h;	93%

4-chloro-aniline (106-47-8) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(4-chlorophenyl)-4-nitro-2,3-dihydroisoindol-1-one (1630974-72-9)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5h; Inert atmosphere;	90%

2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(azidomethyl)-3-nitrobenzoic acid methyl ester (825655-17-2)

Conditions	Yield
With sodium azide In DMF (N,N-dimethyl-formamide); water	89.6%
With sodium azide In DMF (N,N-dimethyl-formamide); water	89.6%

2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) + 2-aminocaprolactam (21568-87-6) → 4-nitro-2-[(3S)-2-oxoazepan-3-yl]isoindoline-1-one

Conditions	Yield
With triethylamine In N,N-dimethyl-formamide at 50℃; for 18h;	89%

2-methoxyethylamine (109-85-3) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(2-methoxyethyl)-4-nitro-2,3-dihydro-isoindol-1-one (1381925-34-3)

Conditions	Yield
In toluene for 1h; Product distribution / selectivity; Reflux;	88%

3-iodobenzylamine (696-40-2) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(3-iodobenzyl)-4-nitroisoindolin-1-one (958888-81-8)

Conditions	Yield
With triethylamine In metahnol at 20℃; Reflux;	87%

glutamic acid dimethyl ether (6525-53-7, 16422-27-8, 40149-68-6) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-(4-nitro-1-oxo-1,3-dihydroisoindol-2-yl)glutaric acid dimethyl ester (827026-43-7)

Conditions	Yield
With sodium carbonate In N,N-dimethyl-formamide at 45℃; for 16h; Reagent/catalyst; Solvent;	86.3%
With sodium hydrogencarbonate In acetonitrile Heating / reflux;	78%

(R)-2-aminopropan-1-ol (35320-23-1) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 2-((R)-2-hydroxy-1-methyl-ethyl)-4-nitro-2,3-dihydroisoindol-1-one (1381925-26-3)

Conditions	Yield
In toluene at 20 - 50℃; for 24h; Product distribution / selectivity;	86%

p-methoxybenzylmercaptan (6258-60-2) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → methyl 2-(((4-methoxybenzyl)thio)methyl)-3-nitrobenzoate

Conditions	Yield
Stage #1: p-methoxybenzylmercaptan With triethylamine In dichloromethane at 20℃; for 0.5h; Stage #2: 2-bromomethyl-3-nitro-benzoic acid methyl ester In dichloromethane at 20℃;	86%

(S)-tert-butyl 4,5-diamino-5-oxopentanoate hydrochloride + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → C17H21N3O6

Conditions	Yield
With triethylamine In acetonitrile at 75℃; Inert atmosphere;	83%

3-amino(piperidine-3,5,5-d3)-2,6-dione + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 3-(4-nitro-1-oxoisoindolin-2-yl)(piperidine-3,5,5-d3)-2,6-dione (1620016-92-3)

Conditions	Yield
With sodium carbonate In N,N-dimethyl acetamide at 20℃; for 18h;	81%

C12H15(2)HN2O3*ClH + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → C20H18(2)HN3O6

Conditions	Yield
With triethylamine In acetonitrile at 75℃; Inert atmosphere;	81%

2-amino-3-tert-butoxypropionic acid (17083-25-9) + 2-bromomethyl-3-nitro-benzoic acid methyl ester (98475-07-1) → 3-(4-nitro-1-oxoisoindolin-2-yl)piperidine-2,6-dione (827026-45-9)

Conditions	Yield
Stage #1: 2-amino-3-tert-butoxypropionic acid; 2-bromomethyl-3-nitro-benzoic acid methyl ester With sodium hydrogencarbonate In acetonitrile at 5 - 20℃; Reflux; Stage #2: With hydrogenchloride In water at 58 - 62℃; for 4.16667h; pH=< 6; Temperature; Time;	79.5%

Upstream product

• 1975-50-4 2-methyl-3-nitrobenzic acid 
• 109-69-3 n-Butyl chloride 
• 59382-59-1 2-methyl-3-nitro-benzoic acid methyl ester 
• 60-29-7 diethyl ether 
• 62621-09-4 methyl 2-methyl-4-nitrobenzoate 
• 94-36-0 dibenzoyl peroxide 

Downstream Products

• 827026-45-9 3-(4-nitro-1-oxoisoindolin-2-yl)piperidine-2,6-dione 
• 455260-00-1 2-[4-(4-fluoro-benzyl)piperidin-1-ylmethyl]-3-nitro-benzoic acid methyl ester 
• 827026-43-7 2-(4-nitro-1-oxo-1,3-dihydroisoindol-2-yl)glutaric acid dimethyl ester 
• 183270-21-5 2-(2,3-Dimethylphenyl)-4-nitroisoindolin-1-one 
• 1090902-91-2 2-(3-isopropenyl-2-oxo-2,3-dihydro-benzoimidazol-1-ylmethyl)-3-nitro-benzoic acid methyl ester 
• 1381925-13-8 N-[5-Chloro-2-((R)-2-hydroxy-1-methyl-ethyl)-1-oxo-2,3-dihydro-1H-isoindol-4-yl]-2-(4-fluoro-3-trifluoromethyl-phenyl)-acetamide 
• 1381925-30-9 4-fluoro-N-[2-(2-methoxy-1-methyl-ethyl)-1-oxo-2,3-dihydro-1H-isoindol-4-yl]-3-trifluoromethyl-benzamide 
• 1284883-19-7 4-amino-2-(2-methoxy-1-ethyl)-2,3-dihydro-isoindol-1-one 
• 1381925-38-7 N-[5-chloro-2-((R)-2-methoxy-1-methyl-ethyl)-1-oxo-2,3-dihydro-1H-isoindol-4-yl]-4-fluoro-3-trifluoromethyl-benzamide 
• 1449603-74-0 5-(4-methoxybenzyl)-9-(4-nitro-1-oxoisoindolin-2-yl)-2-oxa-5-azaspiro[3.5]nonan-6-one 
• 444289-22-9 N-(2-(2,6-dioxopiperidin-3-yl)-1-oxoisoindolin-4-yl)benzamide 

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