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

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

Uses

Used in Pharmaceutical Industry:
AZODICARBOXYLIC ACID DIMETHYL ESTER is used as a reagent for the synthesis of 2,3-benzodiazepines, which are important in the development of various pharmaceutical products. The compound contributes to the creation of these bioactive molecules, which have potential applications in the treatment of anxiety, insomnia, and other related conditions. Its role in the synthesis process is crucial for the production of effective and safe medications.

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

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

Downstream Products

• 88754-66-9 2,5-dioxa-adipic acid dimethyl ester 
• 553-90-2 Dimethyl oxalate 
• 616-38-6 carbonic acid dimethyl ester 
• 248281-97-2 [Pd(P(C₆H₅)3)C₆H₄C(C₆H₅)NCH(CO₂C₂H₅)N(CO₂CH₃)N(CO₂CH₃)] 
• 1400564-51-3 C₁₅H₁₈N₄O₅ 
• 71805-64-6 5,5-dimethylbicyclo<2.1.0>pentane 
• 153620-25-8 C₁₇H₁₇⁽²⁾H₃N₂O₄ 
• 153620-28-1 7-(2,2-Dimethyl-1-phenyl-propylidene)-2,3-diaza-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid dimethyl ester 
• 7309-66-2 dimethyl 3,6-dihydropyridazine-1,2-dicarboxylate 
• 86358-60-3 C₁₉H₂₇N₅O₉ 
• 100102-72-5 N¹-<(2,5,5-Trimethyl-1,3,6-heptatrienyl)methyl>-N¹,N²-hydrazindicarbonsaeure-dimethylester 
• 100102-71-4 9-<1,2-Bis(methoxycarbonyl)hydrazinomethyl>-3,3,8-trimethyl-6,7-diazatricyclo<3.2.2.0^2,4>non-8-en-6,7-dicarbonsaeure-dimethylester 
• 17643-54-8 N,N'-Bis-(methoxycarbonyl)-hydrazin 
• 77026-72-3 2C₈H₁₀O₄*C₄H₈N₂O₄ 

Relevant articles and documents

Mild and catalytic transesterification reaction using K2HPO 4 for the synthesis of methyl esters

K2HPO4 is an efficient catalyst for the transesterification reaction to produce methyl esters. Various functional groups are compatible under the mild reaction conditions. Georg Thieme Verlag Stuttgart New York.

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.

Methoxy- and Aminoisocyanate

Methoxyisocyanate (1) can be prepared by photolysis of methyl azidoformate (3) or pyrolysis of N-methoxycarbonyl-O-methylhydroxylamine (4).Aminoisocyanate (2) is similarly formed on photolysis of carbamoyl azide (12) and pyrolysis of either methyl carbazate (13) or 3,4-diaminofurazan (14).The infrared spectra of 1 and 2 in an argon matrix at 10 K have been measured, and some of their properties are discussed. - Keywords: Flash pyrolysis/ Matrix IR spectroscopy/ Photolysis