78-67-1

Basic information

• Product Name: 2,2'-Azobis(2-methylpropionitrile)
• Synonyms: A,A'-AZOISOBUTYRONITRILE;AIBN;ALPHA,ALPHA'-AZOBISISOBUTYRONITRILE;ALPHA,ALPHA-AZOBISISOBUTYRONITRILE;ALPHA,ALPHA'-AZO-DI-ISO-BUTYRONITRILE;ALPHA,ALPHA'-AZOISOBUTYRONITRILE;2,2'-dicyano-2,2'-azopropane;2,2'-Dimethyl-2,2'-azodipropionitrile
• CAS NO: 78-67-1
• Molecular Formula: C₈H₁₂N₄
• Molecular Weight: 164.21
• EINECS: 201-132-3
• Product Categories: Free Radical Initiators;Organics;pharmacetical
• Mol File: 78-67-1.mol

Chemical Properties

• Melting Point: 102-104 °C (dec.)(lit.)
• Boiling Point: 281.68°C (rough estimate)
• Flash Point: 4℃
• Appearance: white solid
• Density: 1.11
• Vapor Pressure: 0.81Pa at 24.85℃
• Refractive Index: n20/D1.495
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• Water Solubility: Insoluble
• Stability: Stability Flammable solid. Shock sensitive. Thermally unstable. May be explosive in combination with acetone or heptane. Incompa
• Merck: 13,920
• BRN: 1708400
• CAS DataBase Reference: 2,2'-Azobis(2-methylpropionitrile)(CAS DataBase Reference)
• NIST Chemistry Reference: 2,2'-Azobis(2-methylpropionitrile)(78-67-1)
• EPA Substance Registry System: 2,2'-Azobis(2-methylpropionitrile)(78-67-1)

Safety Data

• Hazard Codes: E,Xn,F,Xi
• Statements: 2-11-20/22-52/53-67-65-48/20-38-63-66-36
• Safety Statements: 39-41-47-61-62-36/37-16-26
• RIDADR: UN 3234 4.1
• WGK Germany: 2
• RTECS: UG0800000
• F: 4.4
• HazardClass: 4.1
• PackingGroup: II
• Hazardous Substances Data: 78-67-1(Hazardous Substances Data)

Synthetic route

2,2'-hydrazobis(2-methylpropionitrile) (6869-07-4) → 2,2'-azobis(isobutyronitrile) (78-67-1)

Conditions	Yield
With potassium hydroxide; potassium hexacyanoferrate(III); pyrographite In dichloromethane at 40℃; for 6h;	99.5%
With hydrogenchloride; molybdophosphoric acid hydrate; dihydrogen peroxide; sodium docusate; sodium bromide In water at 16 - 17℃; for 4.5h; Reagent/catalyst;	95%
With dihydrogen peroxide In acetonitrile at 20℃; Temperature; Solvent;	95.6%

cetyltrimethylammonium chloride (112-02-7) + 2-amino-2-cyanopropane (19355-69-2) → 2,2'-azobis(isobutyronitrile) (78-67-1)

Conditions	Yield
With sodium hypochlorite	93.8%

2,2'-dimethyl-2,2'-hydrazo-di-butyronitrile (171915-82-5) → 2,2'-azobis(isobutyronitrile) (78-67-1)

Conditions	Yield
With oxygen; tetra-N-butylammonium tribromide; sodium nitrite In 1,4-dioxane; water at 60℃; under 760.051 Torr; for 4h; Sealed tube;	72%

bis-(1-chloro-1-methyl-ethyl)-diazene (29540-62-3) + sodium cyanide (143-33-9) → 2,2'-azobis(isobutyronitrile) (78-67-1)

2-amino-2-cyanopropane (19355-69-2) → 2,2'-azobis(isobutyronitrile) (78-67-1)

Conditions	Yield
With sodium hypochlorite
With calcium hypochlorite
With oxygen; 1.5% Au/TiO2 In toluene at 100℃; under 2250.23 - 3750.38 Torr; for 40h;	46 %Chromat.

2,2'-hydrazobis(2-methylpropionitrile) (6869-07-4) + benzene (71-43-2) + dibenzoyl peroxide (94-36-0) → 2,2'-azobis(isobutyronitrile) (78-67-1)

α,α'-(dinitroso-hydrazo)-di-isobutyronitrile + water (7732-18-5) → 2,2'-azobis(isobutyronitrile) (78-67-1)

Conditions	Yield
at 60℃;

hydrazoisobutyric acid dinitrile → 2,2'-azobis(isobutyronitrile) (78-67-1)

Conditions	Yield
With hydrogenchloride; ethanol; bromine

2,2'-hydrazobis(2-methylpropionitrile) (6869-07-4) + benzene (71-43-2) + sodium peroxybenzoate → 2,2'-azobis(isobutyronitrile) (78-67-1)

dimethyl ditelluride (20334-43-4) + 2,2'-azobis(isobutyronitrile) (78-67-1) + methacrylic acid methyl ester (80-62-6) → poly(methyl methacrylate), -C(CN)(CH3)2 and -TeMe terminated, Mn 13100 by GPC, PDI 1.55 by GPC; monomer(s): methyl methacrylate; azoisobutyronitrile; dimethyl ditelluride

Conditions	Yield
at 80℃; for 0.5h;	100%

2,2'-azobis(isobutyronitrile) (78-67-1) + acrylic acid n-butyl ester (141-32-2) → poly(n-butyl acrylate), -C(CN)(CH3)2 and -deuterium terminated, Mn 4400 by GPC, PDI 1.19 by GPC and Mn 4300 by MALDI-TOF-MS, PDI 1.16 by MALDI-TOF-MS; monomer(s): n-butyl acrylate; azoisobutyronitrile

Conditions	Yield
Stage #1: 2,2'-azobis(isobutyronitrile); acrylic acid n-butyl ester With dimethyl ditelluride at 90℃; Stage #2: With 2,2'-azobis(isobutyronitrile); tributyltin deuteride In various solvent(s) at 80℃;	99%

2,2'-azobis(isobutyronitrile) (78-67-1) + biphenyl-4-carboxylic acid (92-92-2) → N-(2-cyanopropan-2-yl)-N-isobutyrylbiphenyl-4-carboxamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	99%

2,2'-azobis(isobutyronitrile) (78-67-1) + 2-Iodobenzoic acid (88-67-5) → N-(2-cyanopropan-2-yl)-2-iodo-N-isobutyrylbenzamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	99%

2,2'-azobis(isobutyronitrile) (78-67-1) + N,N-di-p-tolylmethacrylamide → C22H24N2O

Conditions	Yield
With copper(l) iodide In dichloromethane at 80℃; for 24h; Inert atmosphere;	99%

2,2'-azobis(isobutyronitrile) (78-67-1) + N,N’-dimethyl-N,N’-di(4-pyridinyl)thiuram disulfide (1158958-94-1) → 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate (1158958-96-3)

Conditions	Yield
In ethyl acetate for 16h; Reflux;	98.4%
In ethyl acetate for 16h; Reflux;	88%

pyridine (110-86-1) + 2,2'-azobis(isobutyronitrile) (78-67-1) → C18H22N6O12S4

Conditions	Yield
With sulfur trioxide In dichloromethane for 24h;	98%

2,2'-azobis(isobutyronitrile) (78-67-1) + p-Toluic acid (99-94-5) → N-(2-cyanopropan-2-yl)-N-isobutyryl-4-methylbenzamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	98%

2,2'-azobis(isobutyronitrile) (78-67-1) + 4-(1,1-dimethylethyl)benzoic acid (98-73-7) → 4-tert-Butyl-N-(2-cyanopropan-2-yl)-N-isobutyrylbenzamideWhite

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	98%

2,2'-azobis(isobutyronitrile) (78-67-1) + 2-iodoyl-5-methylbenzoic acid (52548-14-8) → N-(2-cyanopropan-2-yl)-2-iodo-N-isobutyryl-5-methylbenzamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	98%

2,2'-azobis(isobutyronitrile) (78-67-1) + 5-methyl-N-(quinolin-8-yl)thiophene-2-carboxamide → 3-cyano-5-methyl-N-(quinolin-8-yl)thiophene-2-carboxamide

Conditions	Yield
With copper(II) nitrate hydrate; oxygen; silver(I) acetate In acetonitrile at 130℃; for 8h; Sealed tube; regioselective reaction;	98%

2,2'-azobis(isobutyronitrile) (78-67-1) + N-(2-naphthalenecarbonyl)-8-aminoquinoline (444079-13-4) → 2-(quinolin-8-yl)-1H-benzo[f]isoindole-1,3(2H)-dione

Conditions	Yield
With copper(II) nitrate hydrate; oxygen; silver(I) acetate In acetonitrile at 130℃; for 8h; Sealed tube; regioselective reaction;	98%

cobaltocene (1277-43-6) + 2,2'-azobis(isobutyronitrile) (78-67-1) → C5H5CoC5H5C(CH3)2CN

Conditions	Yield
In toluene excess of Co(C5H5)2, complete exclusion of O2, in boiling toluene; mechanism discussed;;	97%
In toluene excess of Co(C5H5)2, complete exclusion of O2, in boiling toluene; mechanism discussed;;	97%
In further solvent(s) further solvent: styrol; excess of Co(C5H5)2, complete exclusion of O2;;	0%

2,2'-azobis(isobutyronitrile) (78-67-1) + 2-Biphenylcarboxylic acid (947-84-2) → N-(2-cyanopropan-2-yl)-N-isobutyrylbiphenyl-2-carboxamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	97%

2,2'-azobis(isobutyronitrile) (78-67-1) + 2-bromobenzoic-acid (88-65-3) → 2-Bromo-N-(2-cyanopropan-2-yl)-N-isobutyrylbenzamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	97%

2,2'-azobis(isobutyronitrile) (78-67-1) + 4-n-methylphenylacetylene (766-97-2) → 3-(4-methylphenyl)-2-propynenitrile (151589-34-3)

Conditions	Yield
With Cu-MOF In acetonitrile at 90℃; for 10h;	97%
With Cu(2+)*C21H10NO6(3-)*C12H10N2*H(1+) In acetonitrile at 90℃; for 8h;	93%
With copper(II) nitrate trihydrate; oxygen In acetonitrile at 80℃; for 12h;

1-ethynyl-4-fluorobenzene (766-98-3) + 2,2'-azobis(isobutyronitrile) (78-67-1) → 3-(4-fluorophenyl)-2-propynenitrile (575433-43-1)

Conditions	Yield
With Cu-MOF In acetonitrile at 90℃; for 8h;	97%
With Cu(2+)*C21H10NO6(3-)*C12H10N2*H(1+) In acetonitrile at 90℃; for 8h;	94%
With copper(II) nitrate trihydrate; oxygen In acetonitrile at 80℃; for 12h;

2,2'-azobis(isobutyronitrile) (78-67-1) + 2-(tert-butylamino)-1-(4-methylphenyl)-2-oxoethyl 3-phenyl-2H-azirine-2-carboxylate → (Z)-2-(tert-butylamino)-1-(4-methylphenyl)-2-oxoethyl 3-amino-3-phenylacrylate

Conditions	Yield
With tri-n-butyl-tin hydride In benzene at 90℃; for 0.5h;	97%

2,2'-azobis(isobutyronitrile) (78-67-1) + diphenyl ditelluride (32294-60-3) + methacrylic acid methyl ester (80-62-6) → poly(methyl methacrylate), -C(CN)(CH3)2 and -TePh terminated, Mn 50100 by GPC, PDI 1.22 by GPC; monomer(s): methyl methacrylate; azoisobutyronitrile; diphenyl ditelluride

Conditions	Yield
Stage #1: 2,2'-azobis(isobutyronitrile); diphenyl ditelluride In various solvent(s) at 80℃; for 3h; Stage #2: methacrylic acid methyl ester In various solvent(s) at 80℃; for 4h;	96%

bis(2,6-dimethylthiobenzoyl) disulfide + 2,2'-azobis(isobutyronitrile) (78-67-1) → 2-cyanoprop-2-yl 2,6-dimethyldithiobenzoate (851729-41-4)

Conditions	Yield
In ethyl acetate for 16h; Heating;	96%

2,2'-azobis(isobutyronitrile) (78-67-1) + C21H18O3 (53151-59-0) → 3-hydroxy-2,2-dimethyl-4-oxo-3,4-diphenylbutyronitrile (1089675-68-2) + 3-hydroxy-2,2-dimethyl-3-phenylpropanenitrile (50654-42-7)

Conditions	Yield
With titanium tetrachloride In benzene at 80℃; for 1.5h; Inert atmosphere;	A 96% B n/a
With titanium tetrachloride In benzene at 80℃; for 1.5h; Inert atmosphere;	A n/a B 71%

2,2'-azobis(isobutyronitrile) (78-67-1) + benzoic acid (65-85-0) → N-(2-cyanopropan-2-yl)-N-isobutyrylbenzamide

Conditions	Yield
In cyclohexane at 80℃; for 12h; Inert atmosphere; Schlenk technique;	96%

2,2'-azobis(isobutyronitrile) (78-67-1) + 5-phenyl-N-(quinolin-8-yl)furan-2-carboxamide → 3-cyano-5-phenyl-N-(quinolin-8-yl)furan-2-carboxamide

Conditions	Yield
With copper(II) nitrate hydrate; oxygen; silver(I) acetate In acetonitrile at 130℃; for 8h; Sealed tube; regioselective reaction;	96%

2,2'-azobis(isobutyronitrile) (78-67-1) + N-quinolin-8-yl-benzamide (33757-48-1) → 2-(quinolin-8-yl)-isoindoline-1,3-dione (19348-61-9)

Conditions	Yield
With copper(II) nitrate hydrate; oxygen; silver(I) acetate In acetonitrile at 130℃; for 8h; Catalytic behavior; Temperature; Reagent/catalyst; Solvent; Time; Sealed tube; regioselective reaction;	96%

2,2'-azobis(isobutyronitrile) (78-67-1) + 4-methyl-N-(quinolin-8-yl)benzamide (33757-49-2) → 5-methyl-2-(quinolin-8-yl)isoindoline-1,3-dione

Conditions	Yield
With copper(II) nitrate hydrate; oxygen; silver(I) acetate In acetonitrile at 130℃; for 8h; Sealed tube; regioselective reaction;	96%

2,2'-azobis(isobutyronitrile) (78-67-1) + phenylacetylene (536-74-3) → 2-cyano-1-phenylacetylene (935-02-4)

Conditions	Yield
With Cu-MOF In acetonitrile at 90℃; for 9h;	96%
With Cu(2+)*C21H10NO6(3-)*C12H10N2*H(1+) In acetonitrile at 90℃; for 8h;	94%
With copper(II) nitrate trihydrate; oxygen In acetonitrile at 80℃; for 12h;

2,2'-azobis(isobutyronitrile) (78-67-1) + 4-cyanophenylacetylene (3032-92-6) → 4-(cyanoethynyl)benzonitrile

Conditions	Yield
With Cu-MOF In acetonitrile at 90℃; for 9h;	96%
With Cu(2+)*C21H10NO6(3-)*C12H10N2*H(1+) In acetonitrile at 90℃; for 8h;	90%

2,2'-azobis(isobutyronitrile) (78-67-1) + 4-ethynyl-1,1'-biphenyl (29079-00-3) → 3-(1,1'-biphenyl)-4-yl-2-propynenitrile

Conditions	Yield
With Cu-MOF In acetonitrile at 90℃; for 9h;	96%
With Cu(2+)*C21H10NO6(3-)*C12H10N2*H(1+) In acetonitrile at 90℃; for 8h;	88%

2,2'-azobis(isobutyronitrile) (78-67-1) + Thiram (137-26-8) → dimethyl-dithiocarbamic acid cyano-dimethyl-methyl ester

Conditions	Yield
In cyclohexane; chlorobenzene for 4h; Heating;	95%
In benzene for 24h; Heating;	93%

Upstream product

• 6869-07-4 2,2'-hydrazobis(2-methylpropionitrile) 
• 29540-62-3 bis-(1-chloro-1-methyl-ethyl)-diazene 
• 143-33-9 sodium cyanide 
• 19355-69-2 2-amino-2-cyanopropane 
• 71-43-2 benzene 
• 94-36-0 dibenzoyl peroxide 
• 7732-18-5 water 
• 112-02-7 cetyltrimethylammonium chloride 
• 171915-82-5 2,2'-dimethyl-2,2'-hydrazo-di-butyronitrile 

Downstream Products

• 6336-46-5 (1,3,3,3-tetrachloro-propyl)-boronic acid dibutyl ester 
• 111589-15-2 N,O-bis-(1-cyano-1-methyl-ethyl)-N-(4-nitro-phenyl)-hydroxylamine 
• 114254-56-7 N-[2-(1-cyano-1-methyl-ethoxy)-4-nitro-phenyl]-N,O-bis-(1-cyano-1-methyl-ethyl)-hydroxylamine 
• 823-78-9 meta-bromobenzyl bromide 
• 3958-57-4 1-bromomethyl-3-nitrobenzene 
• 100-11-8 1-bromomethyl-4-nitro-benzene 
• 108-85-0 1-bromocyclohexane 
• 111-87-5 octanol 
• 109286-26-2 N,O-bis-(1-cyano-1-methyl-ethyl)-N-(3,5-dinitro-phenyl)-hydroxylamine 
• 260-94-6 acridine 
• 52674-05-2 2-(9,10-dihydro-acridin-9-yl)-2-methyl-propionitrile 
• 4838-42-0 9,10,9',10'-tetrahydro-9,9'-biacridyl 
• 78-82-0 Isobutyronitrile 
• 116977-29-8 3-acetoxy-1-acetylsulfanyl-propene 

Relevant articles and documents

Highly efficient oxidation of 2,2′-hydrazobis-isobutyronitrile to 2,2′-Azobis-isobutyronitrile over a CrO: X/TiO2catalyst with hydrogen peroxide

Green oxidation of 2,2′-hydrazobis-isobutyronitrile (HAIBN) to 2,2′-Azobis-isobutyronitrile (AIBN) over a recyclable solid catalyst was a significant challenge. A titanium dioxide-supported chromium oxide (CrOx/TiO2) catalyst was, for the first time, developed for oxidation of HAIBN with hydrogen peroxide and achieved complete conversion of HAIBN with a high (94.8%) yield of AIBN.

PROCESS FOR SYNTHESIZING AZO COMPOUNDS

A process for synthesizing an azo compound by oxidation of a hydrogen compound in the presence of a catalyst and a compound of formula (I) is described in which R1, R2 and R3 [in-line-formulae](R1)(R2)C(PO3(R3)2)2??(I)[/in-line-formulae] are as defined. The use of a compound of formula (I) as complexing agent for a catalyst is also described.

METHOD FOR PRODUCING AZO COMPOUNDS

PROBLEM TO BE SOLVED: To provide a method that can produce azo compounds at good yields by making oxygen or an oxygen-containing gas act on hydrazo groups of hydrazo compounds when oxidatively dehydrogenating them. SOLUTION: Azo compounds are produced by making oxygen or an oxygen-containing gas act on hydrazo compounds in the presence of vanadium or cerium compounds, and a solvent. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

METHOD FOR PRODUCING AZO COMPOUNDS

PROBLEM TO BE SOLVED: To provide a method that can produce azo compounds at good yields by making oxygen or an oxygen-containing gas act on hydrazo compounds when oxidatively dehydrogenating them. SOLUTION: Azo compounds are produced by making oxygen or an oxygen-containing gas act on hydrazo compounds in the presence of nitrite compounds, bromine compounds and a solvent. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

METHOD FOR PRODUCING AZO COMPOUNDS

PROBLEM TO BE SOLVED: To provide a method that can produce azo compounds at good yields by making oxygen or an oxygen-containing gas act on hydrazo compounds when oxidatively dehydrogenating them. SOLUTION: Azo compounds are produced by making oxygen or an oxygen-containing gas act on hydrazo compounds in the presence of at least one compound selected from the group consisting of vanadium and cerium compounds, the oxidation reaction to be performed without using a solvent. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

Azobisisobutyronitrile preparation method

The present invention relates to an azobisisobutyronitrile preparation method, which comprises: carrying out a reaction on sodium hypochlorite, ammonia and acetone to prepare an acetone azine synthesis solution; purifying to obtain acetone azine with a mass content of not less than 90%; reacting with hydrogen cyanide to obtain hydrogenated azobisisobutyronitrile; and oxidizing with chlorine gas orhydrogen peroxide to obtain an azobisisobutyronitrile solution. Compared to the conventional process, the method of the present invention can simplify the production process, shorten the production cycle, and reduce the consumption of steam and circulating water so as to increase the yield of azobisisobutyronitrile and reduce the production cost.

METHOD OF SYNTHESIS OF AZO COMPOUNDS

A process is provided for synthesizing an azo compound, such as AIBN, by oxidation of a hydrazo compound using hydrogen peroxide. This process comprises a step of adding to the reaction medium a particular reducing agent, such as hydrazine.

Metal bridging for directing and accelerating electron transfer as exemplified by harnessing the reactivity of AIBN

A new strategy for tuning the electron transfer between radicals and enolates has been developed. This method elicits the innate reactivity of AIBN with a copper catalyst and enables a cascade reaction with cinnamic acids. Electron paramagnetic resonance studies and control experiments indicate that the redox-active copper species not only activates the radical by coordination, but also serves as a bridge to bring the radical and nucleophile within close proximity to facilitate electron transfer. By exploiting possible combinations of redox-active metals and radical entities with suitable coordinating functional groups, this strategy should contribute to the development of a broad range of radical-based reactions.

PREPARATION OF AZO COMPOUNDS WITH SOLID CATALYSTS

The present invention refers to a procedure for preparing azo compounds comprising a reaction between at least: one amine or polyamine, molecular oxygen, a catalyst comprising at least one support selected from at least a metal oxide of one of the elements of the groups 3, 4, 5, 6, 8, 9, 11 and 13, silica, an anionic laminar compound of hydrotalcite type or its derivatives, active carbon or an organic polymer. In addition, said catalyst may contain nanoparticles of gold.

Method for the production of azo compounds

The invention relates to a method for production of azo compounds. In particular the invention relates to a step-wise method for production of an azo compound, by seeding and oxidation of the corresponding hydrazoic compound.