2446-84-6

Basic information

• Product Name: AZODICARBOXYLIC ACID DIMETHYL ESTER
• Synonyms: METHYL AZODICARBOXYLATE;AZODIFORMIC ACID DIMETHYL ESTER;AZODICARBOXYLIC ACID DIMETHYL ESTER;DIMETHYL DIAZENEDICARBOXYLATE;DIMETHYL AZODICARBOXYLATE;AZODICARBOXYLIC ACID DIMETHYL ESTER (40% IN TOLUENE);Dimethyl Azodicarboxylate (40% in Toluene, ca. 2.7mol/L);1,2-Diazenedicarboxylic acid dimethyl ester
• CAS NO: 2446-84-6
• Molecular Formula: C₄H₆N₂O₄
• Molecular Weight: 146.1
• Product Categories: Aromatic Esters
• Mol File: 2446-84-6.mol
• Article Data: 3

Chemical Properties

• Melting Point: 10°C
• Boiling Point: 84°C 8mm
• Flash Point: 23°C
• Appearance: /
• Density: 0,99 g/cm3
• Vapor Pressure: 0.238mmHg at 25°C
• Refractive Index: 1.4487 (estimate)
• CAS DataBase Reference: AZODICARBOXYLIC ACID DIMETHYL ESTER(CAS DataBase Reference)
• NIST Chemistry Reference: AZODICARBOXYLIC ACID DIMETHYL ESTER(2446-84-6)
• EPA Substance Registry System: AZODICARBOXYLIC ACID DIMETHYL ESTER(2446-84-6)

Safety Data

• Statements: 11-36/37/38
• Safety Statements: 9-16-33
• RIDADR: 1993
• Hazardous Substances Data: 2446-84-6(Hazardous Substances Data)

Usage

Chemical Properties

clear orange-red to brown liquid

Uses

Methyl (NE)-N-methoxycarbonyliminocarbamate is a reagent used in the synthesis of 2,3-benzodiazepines.

InChI:InChI=1/C4H6N2O4/c1-9-3(7)5-6-4(8)10-2/h1-2H3/b6-5+

Synthetic route

methanol (67-56-1) + diethylazodicarboxylate (1972-28-7) → dimethyl azodicarboxylate (2446-84-6)

Conditions	Yield
With dipotassium hydrogenphosphate for 1h; Reflux;	98%

C7H15N3O6Si (135299-67-1) → dimethyl azodicarboxylate (2446-84-6)

Conditions	Yield
In dichloromethane at 25℃; for 72h;	75%

N,N'-Bis-(methoxycarbonyl)-hydrazin (17643-54-8) → dimethyl azodicarboxylate (2446-84-6)

Conditions	Yield
With nitric acid

azidoformiate de methyle (1516-56-9) → formaldehyd (50-00-0) + isocyanic acid (75-13-8) + dimethyl azodicarboxylate (2446-84-6) + methoxy isocyanate (117775-56-1)

Conditions	Yield
Irradiation;

azidoformiate de methyle (1516-56-9) → formaldehyd (50-00-0) + isocyanic acid (75-13-8) + methyleneamine (2053-29-4) + dimethyl azodicarboxylate (2446-84-6) + methoxy isocyanate (117775-56-1) + CO2

Conditions	Yield
Product distribution; Heating; further temp., pressure, residence time;

N,N'-Bis-(methoxycarbonyl)-hydrazin (17643-54-8) + nitric acid (7697-37-2) → dimethyl azodicarboxylate (2446-84-6)

4,2',3'-trimethyl-4'-(p-fluorobenzyl)purpurogallin (946832-61-7) + dimethyl azodicarboxylate (2446-84-6) → C25H25N2O9F

Conditions	Yield
In toluene Heating;	100%

2-(p-fluorobenzyloxy)tropone (1002736-86-8) + dimethyl azodicarboxylate (2446-84-6) → dimethyl 1-(p-fluorobenzyloxy)-2-oxo-6,7-diazabicyclo[3.2.2]nona-3,8-diene-6,7-dicarboxylate

Conditions	Yield
In toluene hetero-Diels Alder reaction; Heating;	100%

2-(o-fluorobenzyloxy)tropone (1002736-87-9) + dimethyl azodicarboxylate (2446-84-6) → dimethyl 1-(o-fluorobenzyloxy)-2-oxo-6,7-diazabicyclo[3.2.2]nona-3,8-diene-6,7-dicarboxylate

Conditions	Yield
In toluene hetero-Diels Alder reaction; Heating;	100%

dimethyl azodicarboxylate (2446-84-6) + 1,3-Bis-(1-cyclopenta-2,4-dienylidene-2,2-dimethyl-propyl)-benzene (153620-13-4) → C34H42N4O8 (153620-14-5)

Conditions	Yield
In dichloromethane for 1h;	99%

C12H13BrN2O + dimethyl azodicarboxylate (2446-84-6) → C15H17BrN4O5

Conditions	Yield
With (η5-1,2,3,4,5-pentamethylcyclopentadienyl)Ir[(S,S)-N-(Ms)-1,2-diphenylethylenediamine] In toluene at 0℃; for 2.33333h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	99%

ethyl 2-(4-chlorophenyl)-2-cyanoacetate (147795-56-0, 15032-43-6) + dimethyl azodicarboxylate (2446-84-6) → C15H16ClN3O6

Conditions	Yield
With C35H45IrN2O3S In toluene at -20℃; for 2h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	99%

Cyan-phenyl-essigsaeure-dimethylamid (1134-20-9) + dimethyl azodicarboxylate (2446-84-6) → C15H18N4O5 (1400564-51-3)

Conditions	Yield
With (η5-1,2,3,4,5-pentamethylcyclopentadienyl)Ir[(S,S)-N-(Ms)-1,2-diphenylethylenediamine] In toluene at 0℃; for 2.33333h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	99%

2-t-butoxycarbonyl-2-phenylacetonitrile (115549-32-1) + dimethyl azodicarboxylate (2446-84-6) → C17H21N3O5

Conditions	Yield
With (η5-1,2,3,4,5-pentamethylcyclopentadienyl)Ir[(S,S)-N-(Ms)-1,2-diphenylethylenediamine] In toluene at 0℃; for 2.33333h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	99%

dimethyl azodicarboxylate (2446-84-6) + 3,4-dihydronaphthalen-1-yl 2,2,2-trifluoroacetate → (R)-dimethyl 1-(1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)hydrazine-1,2-dicarboxylate

Conditions	Yield
With (R)-((4,4’-bi-1,3-benzodioxole)-5,5’-diyl)bis(bis(3,5-di-t-butyl-4-methoxyphenyl))phosphine; 2,2,2-trifluoroethanol; silver trifluoromethanesulfonate In tetrahydrofuran; N,N-dimethyl-formamide at -78 - 20℃; for 15h; Reagent/catalyst; Solvent; Temperature; Inert atmosphere; Darkness; enantioselective reaction;	99%

C13H11F3O2 (1408247-07-3) + dimethyl azodicarboxylate (2446-84-6) → dimethyl 1-(5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulen-6-yl)hydrazine-1,2-dicarboxylate

Conditions	Yield
With (R)-((4,4’-bi-1,3-benzodioxole)-5,5’-diyl)bis(bis(3,5-di-t-butyl-4-methoxyphenyl))phosphine; 2,2,2-trifluoroethanol; silver trifluoromethanesulfonate In tetrahydrofuran; N,N-dimethyl-formamide at -78 - 20℃; for 16h; Inert atmosphere; Darkness; enantioselective reaction;	99%

C13H11F3O3 (130399-99-4) + dimethyl azodicarboxylate (2446-84-6) → (R)-dimethyl 1-(6-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)hydrazine-1,2-dicarboxylate

Conditions	Yield
With (R)-((4,4’-bi-1,3-benzodioxole)-5,5’-diyl)bis(bis(3,5-di-t-butyl-4-methoxyphenyl))phosphine; 2,2,2-trifluoroethanol; silver trifluoromethanesulfonate In tetrahydrofuran; N,N-dimethyl-formamide at -78 - 20℃; for 11h; Inert atmosphere; Darkness; enantioselective reaction;	99%

4,2',3'-trimethyl-4'-benzylpurpurogallin (946832-58-2) + dimethyl azodicarboxylate (2446-84-6) → C25H26N2O9

Conditions	Yield
In toluene Heating;	98%

2-methoxytropone (2161-40-2) + dimethyl azodicarboxylate (2446-84-6) → dimethyl 1-methoxy-2-oxo-6,7-diazabicyclo[3.2.2]nona-3,8-diene-6,7-dicarboxylate

Conditions	Yield
In toluene hetero-Diels Alder reaction; Heating;	98%

dimethyl azodicarboxylate (2446-84-6) + 1-phenyl-propan-1-one (93-55-0) → dimethyl 1-(1-oxo-1-phenylpropan-2-yl)hydrazine-1,2-dicarboxylate (86358-61-4)

Conditions	Yield
With 1,2,2,6,6-pentamethylpiperidine; tris(pentafluorophenyl)borate In toluene at 22℃; for 12h; Inert atmosphere;	98%

dimethyl azodicarboxylate (2446-84-6) + 1-methyl-pyrrolidine-2-thione (10441-57-3) → dimethyl 1-(1-methyl-2-thioxopyrrolidin-3-yl)hydrazine-1,2-dicarboxylate

Conditions	Yield
With 1,2,2,6,6-pentamethylpiperidine; tris(pentafluorophenyl)borate In toluene at 22℃; for 12h; Inert atmosphere;	98%

N1-<(2,5,5-Trimethyl-1,3,6-heptatrienyl)methyl>-N1,N2-hydrazindicarbonsaeure-dimethylester (100102-72-5) + dimethyl azodicarboxylate (2446-84-6) → 9-<1,2-Bis(methoxycarbonyl)hydrazinomethyl>-3,3,8-trimethyl-6,7-diazatricyclo<3.2.2.02,4>non-8-en-6,7-dicarbonsaeure-dimethylester (100102-71-4)

Conditions	Yield
In benzene at 50℃; for 5h;	97%

4-hydroxy-2,3,6-trimethoxy-5H-benzo[7]annulen-5-one (15795-64-9) + dimethyl azodicarboxylate (2446-84-6) → C18H20N2O9

Conditions	Yield
In toluene Heating;	97%

inden-1-one (83-33-0) + dimethyl azodicarboxylate (2446-84-6) → dimethyl 1-(1-oxo-2,3-dihydro-1H-inden-2-yl)hydrazine-1,2-dicarboxylate

Conditions	Yield
With 1,2,2,6,6-pentamethylpiperidine; tris(pentafluorophenyl)borate In toluene at 22℃; for 12h; Inert atmosphere;	97%

Thiobutyrolactone (1003-10-7) + dimethyl azodicarboxylate (2446-84-6) → dimethyl 1-(2-oxotetrahydrothiophen-3-yl)hydrazine-1,2-dicarboxylate

Conditions	Yield
With 1,2,2,6,6-pentamethylpiperidine; tris(pentafluorophenyl)borate In toluene at 22℃; for 12h; Inert atmosphere;	97%

α-(1-dimethylaminovinyl)pyridine (14548-17-5) + dimethyl azodicarboxylate (2446-84-6) → C17H24N6O8 (86358-58-9)

Conditions	Yield
In diethyl ether overnight;	96%

2-tert-Butyl-2H-isoindol (55023-87-5) + dimethyl azodicarboxylate (2446-84-6) → C20H27N5O8 (76670-59-2)

Conditions	Yield
	96%

2-methyl-3-pyrrolidin-1-yl-5,6-dihydro-4H-thiopyran 1,1-dioxide (344417-07-8) + dimethyl azodicarboxylate (2446-84-6) → 4-(N,N'-dimethoxycarbonylhydrazino)-2-methyl-3-pyrrolidin-1-yl-5,6-dihydro-4H-thiopyran 1,1-dioxide (89717-32-8)

Conditions	Yield
In benzene for 72h; Ambient temperature;	96%

dimethyl azodicarboxylate (2446-84-6) + acetophenone (98-86-2) → dimethyl 1-(1-phenylvinyl)-1,2-hydrazinedicarboxylate

Conditions	Yield
With triphenylphosphine In dichloromethane at 20℃; for 24h; Mitsunobu reaction;	96%

4,2',3'-trimethyl-4'-(o-fluorobenzyl)purpurogallin (946832-64-0) + dimethyl azodicarboxylate (2446-84-6) → C25H25N2O9F

Conditions	Yield
In toluene Heating;	96%

4,2',3'-trimethyl-4'-(p-methoxybenzyl)purpurogallin (946832-69-5) + dimethyl azodicarboxylate (2446-84-6) → C26H28N2O10

Conditions	Yield
In toluene Heating;	96%

dimethyl azodicarboxylate (2446-84-6) + (+)-(1R,6R)-3,7,7-Trimethyl-4-methylenbicyclo<4.1.0>hept-2-en (103200-82-4, 106007-94-7) → 9-<1,2-Bis(methoxycarbonyl)hydrazinomethyl>-3,3,8-trimethyl-6,7-diazatricyclo<3.2.2.02,4>non-8-en-6,7-dicarbonsaeure-dimethylester (100102-71-4)

Conditions	Yield
In benzene at 50℃; for 5h;	95%

dimethyl azodicarboxylate (2446-84-6) + 6-<5-methoxy-3,3-dimethyl-2-tetrahydrofuranyl>fulvene (98330-87-1) → N,N'-bis(methoxycarbonyl)-2,3-diaza-7-<5-methoxy-3,3-dimethyl-2-tetrahydrofuranylidene>bicyclo<2.2.1>hept-5-ene (110528-18-2, 110610-86-1, 110610-87-2, 110610-88-3)

Conditions	Yield
In diethyl ether at 4℃; for 120h;	95%

dimethyl azodicarboxylate (2446-84-6) + acetic p-nitrophenyldiazoacetic anhydride (101137-77-3) → Acetyl-[[(E)-methoxycarbonylimino]-(4-nitro-phenyl)-methyl]-carbamic acid methyl ester

Conditions	Yield
dirhodium tetraacetate In benzene at 50℃;	95%

2,3,4,6-tetramethoxy-5H-benzo[7]annulen-5-one (6273-57-0) + dimethyl azodicarboxylate (2446-84-6) → C19H22N2O9

Conditions	Yield
In toluene Heating;	95%

Upstream product

• 17643-54-8 N,N'-Bis-(methoxycarbonyl)-hydrazin 
• 7697-37-2 nitric acid 
• 67-56-1 methanol 
• 1972-28-7 diethylazodicarboxylate 
• 1516-56-9 azidoformiate de methyle 
• 135299-67-1 C₇H₁₅N₃O₆Si 

Downstream Products

• 176174-45-1 1-benzylideneamino-5-(1,2-dimethoxycarbonyl)hydrazino-2-methylthio-4-phenyl-1H-imidazole 
• 1190589-10-6 C₂₇H₂₅N₅O₇S 
• 66750-61-6 dimethyl 1-(2-methoxy-2-oxo-1-phenylethyl)hydrazine-1,2-dicarboxylate 
• 72990-97-7 dimethyl 1-(2-methyl-1-oxo-1-phenylpropan-2-yl)hydrazine-1,2-dicarboxylate 
• 86358-61-4 dimethyl 1-(1-oxo-1-phenylpropan-2-yl)hydrazine-1,2-dicarboxylate 

Relevant articles and documents

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N-NITROHYDRAZINES AND THEIR SALTS

A method was developed for the synthesis of functionally substituted N-nitrohydrazines by nonacid nitration of the respective silylhydrazines.It was shown that the stability of these compounds increases with increase in the number of electronegative substituents.The first representative of N,N'-dinitrohydrazines, i.e., N,N'-dinitro-N,N'-diacetylhydrazine, was synthesized.Some of the obtained N-nitrohydrazines are characterized by dissociation with the formation of diazenes.The action of nucleophilic reagents on functionally N,N'-disubstituted N-methyl-N'-nitrohydrazines gave the salts of N-nitrohydrazines.