2638-94-0

Basic information

• Product Name: 4,4'-Azobis(4-cyanovaleric acid)
• Synonyms: 4'-Azobis(4-cyanovaleric acid);(E)-4,4'-(diazene-1,2-diyl)bis(4-cyanopentanoic acid);4,4'-Azobis(4-cyanovaleric acid) >=98.0% (T);4,4'-Azobis(4-cyanovaleric acid) >=75%;4,4’-Azobis-(4-cyanopentanoic;4,4’-azobis(4-cyano-pentanoicaci;4,4’-azobis(4-cyano-valericaci;4,4’-azobis[4-cyano-pentanoicaci
• CAS NO: 2638-94-0
• Molecular Formula: C₁₂H₁₆N₄O₄
• Molecular Weight: 280.28
• EINECS: 220-135-0
• Product Categories: Industrial/Fine Chemicals;Organic acids;Azo/Diazo Compounds;Building Blocks;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks
• Mol File: 2638-94-0.mol

Chemical Properties

• Melting Point: 118-125 °C (dec.)(lit.)
• Boiling Point: 423°C (rough estimate)
• Flash Point: 258.3 °C
• Appearance: white crystalline powder
• Density: 1.2464 (rough estimate)
• Refractive Index: 1.6081 (estimate)
• Storage Temp.: 2-8°C
• PKA: 3.98±0.10(Predicted)
• Water Solubility: Soluble in water.
• Sensitive: Light Sensitive
• BRN: 1729856
• CAS DataBase Reference: 4,4'-Azobis(4-cyanovaleric acid)(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4'-Azobis(4-cyanovaleric acid)(2638-94-0)
• EPA Substance Registry System: 4,4'-Azobis(4-cyanovaleric acid)(2638-94-0)

Safety Data

• Hazard Codes: F
• Statements: 11
• Safety Statements: 15-16-22-24/25-36
• RIDADR: UN 1325 4.1/PG 2
• WGK Germany: 2
• RTECS: YV6190500
• F: 4.4-8
• TSCA: Yes
• HazardClass: 4.1
• Hazardous Substances Data: 2638-94-0(Hazardous Substances Data)

Usage

Uses

Used in Polymer Synthesis:
4,4'-Azobis(4-cyanovaleric acid) is used as a free radical initiator in the synthesis of polymers such as polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, and synthetic fibers. It is particularly effective in both heterogeneous and homogeneous free-radical polymerizations, as well as in reversible addition-fragmentation chain transfer (RAFT) polymerization.
Used in Plastics and Elastomers:
In the plastics and elastomers industry, 4,4'-Azobis(4-cyanovaleric acid) is utilized as a blowing agent, contributing to the expansion and formation of the desired material properties.
Used in the Preparation of Polystyrene Particles:
4,4'-Azobis(4-cyanovaleric acid) has been employed in the preparation of polystyrene particles by polymerizing styrene in ethyl alcohol, which is an essential process in the production of various polystyrene-based materials.

Hazard

Toxic.

Flammability and Explosibility

Notclassified

Biochem/physiol Actions

4,4′-azobis(4-cyanovaleric acid) is an azo-initiator that induces lipid peroxidation of sunflower oil.

Safety Profile

Moderately toxic byintraperitoneal route. When heated to decomposition itemits toxic vapors of NOx.

Synthetic route

4,4'-hydrazo-bis-4-cyano-pentanoic acid → 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0)

Conditions	Yield
With oxone; potassium bromide In water at 20℃;	26%

sodium cyanide (143-33-9) + levulinic acid (123-76-2) → 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0)

Conditions	Yield
With sulfuric acid; water; hydrazine Behandeln des Reaktionsgemisches mit Brom; optically inactive stereoisomer(ic) of mp: 111 degree;
With sulfuric acid; water; hydrazine Behandeln des Reaktionsgemisches mit Brom; optically inactive stereoisomer(ic) of mp: 128 degree;

1-hydroxy-pyrrolidine-2,5-dione (6066-82-6) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-Cyano-4-[1-cyano-3-(2,5-dioxo-pyrrolidin-1-yloxycarbonyl)-1-methyl-propylazo]-4-methyl-butyric acid 2,5-dioxo-pyrrolidin-1-yl ester (130468-55-2)

Conditions	Yield
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 0 - 20℃; for 37h;	98%
With dicyclohexyl-carbodiimide In 1,4-dioxane at 15 - 20℃; for 16h;

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → chloride of 4,4'-azo-bis(4-cyanopentanoic) acid chloride (17170-81-9)

Conditions	Yield
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 3h;	95.6%
With thionyl chloride at 80℃; for 0.666667h;	93%
With phosphorus pentachloride In chloroform at 0 - 20℃;	84%

bis(9H-carbazole-9-yl-thiocarbonyl)disulfide + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → C19H16N2O2S2

Conditions	Yield
In ethyl acetate for 18h; Inert atmosphere; Reflux;	95.4%

2-(N-tert-butoxycarbonylamino)ethanol (26690-80-2) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → bis(2-((tert-butoxycarbonyl)amino)ethyl)(4,4-azobis(4-cyanovalerate))

Conditions	Yield
With dmap In acetonitrile at 0 - 20℃; for 24h;	95%

n-Pent-4-enyl alcohol (821-09-0) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → C22H32N4O4

Conditions	Yield
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 24h; Inert atmosphere; Darkness;	92%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + bis(dodecylsulfanyl thiocarbonyl)disulfide (870532-86-8) → 4-cyano-4-[(dodecylsulfanylthiocarbonyl)-sulfanyl]pentanoic acid (870196-80-8)

Conditions	Yield
In ethyl acetate for 16h; Heating / reflux;	91%
In ethyl acetate for 22h; Reflux;	91%
In ethyl acetate for 18h; Reflux;	76%
In ethyl acetate for 22h; Reflux;	4.162 g
With ethyl acetate for 20h; Reflux;

carbon disulfide (75-15-0) + 1-thiopropane (107-03-9) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-cyano-4-[(propylsulfanylthiocarbonyl)sulfanyl]pentanoic acid

Conditions	Yield
Stage #1: carbon disulfide; 1-thiopropane With potassium hydroxide In water; acetone at 20℃; for 2h; Stage #2: With p-toluenesulfonyl chloride In acetone for 1h; Stage #3: 4,4'-dicyano-4,4'-azo-di-valeric acid at 80℃;	90%

bis(ethylsulfanyl thiocarbonyl)disulfide (10219-97-3) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → cyano-4-[(ethylsulfanylthiocarbonyl)sulfanyl]-4-methylbutanoic acid (1137725-46-2)

Conditions	Yield
In ethyl acetate Reflux; Inert atmosphere;	88%
In ethyl acetate for 12h; Reflux;	87%
In ethyl acetate at 80℃; for 13h; Cooling with ice; Sealed tube; Inert atmosphere;	82%

2,3,4,5,6-pentafluorophenol (771-61-9) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → bis(pentafluorophenyl)azobis(4-cyanovalerate)

Conditions	Yield
With 2,6-dimethylpyridine; trifluoroacetic anhydride In dichloromethane at 0℃; for 24h; Inert atmosphere;	88%

thiazolidine-2-thione (134469-06-0) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 2-[1-cyano-1-methyl-4-oxo-4-(2-thioxo-thiazolidin-3-yl)-butylazo]-2-methyl-5-oxo-5-(2-thioxothiazolidin-3-yl)-pentanenitrile (870779-03-6)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In 1,4-dioxane at 20℃;	86.3%
Stage #1: thiazolidine-2-thione; 4,4'-dicyano-4,4'-azo-di-valeric acid With dmap In dichloromethane for 0.25h; Cooling with ice; Stage #2: With diisopropyl-carbodiimide In dichloromethane at 20℃; for 0.25h;	76.2%
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + triphenylmethyl diethoxyphosphoryldithioformate (178878-92-7) → 4-carboxy-2-cyanobut-2-yl diethoxyphosphoryldithioformate

Conditions	Yield
In ethyl acetate for 15h; Heating;	85%

carbon disulfide (75-15-0) + 1-butanethiol (109-79-5) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4(((butylthio)carbonthioyl)thio)-4-cyanopentanoic acid (937162-86-2)

Conditions	Yield
Stage #1: n-butanethiol With potassium hydroxide In water for 0.5h; Stage #2: carbon disulfide In water for 0.666667h; Stage #3: 4,4'-dicyano-4,4'-azo-di-valeric acid Further stages;	85%

polymer, obtained by reversible addition fragmentation chain-transfer; monomer(s): 4-cyanopentanoic acid dithiobenzoate + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → polymer, Mn (SEC) = 23500, PDI (SEC) = 1.05; monomer(s): 4-cyanopentanoic acid dithiobenzoate; 4,4'-azobis(4-cyanopentanoic acid) + 4-cyano-4-(thiobenzoylthio)pentanoic acid (201611-92-9)

Conditions	Yield
In methanol at 80℃; for 3h;	A 82% B n/a

styrene (100-42-5) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → polymer

Conditions	Yield
With propiononitrile at 90℃;	80%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + 2'-(2''-methylacryolyloxy)ethyl-β-D-galactopyranoside (21698-14-6) + 4-cyano-4-(thiobenzoylthio)pentanoic acid (201611-92-9) → poly[2-(β-D-galactosyloxy)ethyl methacrylate], Mn (SEC) 24100, PDI (SEC) 1.09; monomer(s): 2-(β-D-galactosyloxy)ethyl methacrylate; 4,4-azobis(4-cyanopentanoic acid); 4-(cyanopentanoic acid)-4-dithiobenzoate

Conditions	Yield
In ethanol; water at 70℃; for 3h;	80%

bis(2-phenylethanesulfanylthiocarbonyl)disulfide (1351859-45-4) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-cyano-4-((2-phenylethylsulfanylthiocarbonyl)sulfanyl)pentanoic acid (1351859-46-5)

Conditions	Yield
In ethyl acetate for 18h; Inert atmosphere; Reflux;	78%
In ethyl acetate for 18h; Inert atmosphere; Reflux;	78%
In ethyl acetate for 18h; Inert atmosphere; Reflux;

bis-ethoxythiocarbonyldisulfane (502-55-6) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-cyano-4-((thioethoxyl)sulfanyl)pentanoic acid (220575-22-4)

Conditions	Yield
In 1,4-dioxane for 4h; Heating;	77%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + 1-hydroxy-2-phenyl-2-(4-tert-butoxycarbonylamino-2,2,6,6-tetramethyl-1-piperidinyloxy)ethane (213994-50-4) → 4-{3-[2-(4-tert-Butoxycarbonylamino-2,2,6,6-tetramethyl-piperidin-1-yloxy)-2-phenyl-ethoxycarbonyl]-1-cyano-1-methyl-propylazo}-4-cyano-4-methyl-butyric acid 2-(4-tert-butoxycarbonylamino-2,2,6,6-tetramethyl-piperidin-1-yloxy)-2-phenyl-ethyl ester

Conditions	Yield
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide; N-ethyl-N,N-diisopropylamine In tetrahydrofuran for 8h; Ambient temperature;	76%

bis(thiobenzoyl) disulfide (5873-93-8) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-cyano-4-(thiobenzoylthio)pentanoic acid (201611-92-9)

Conditions	Yield
In ethyl acetate at 85℃; for 12h; Inert atmosphere;	75%
In ethyl acetate for 18h; Heating;	68%
In ethyl acetate Reflux;	65%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + Propargylamine (2450-71-7) → 4-cyano-4-(1-cyano-3-ethynylcarbamoyl-1-methylpropylazo)-N-ethynyl-4-methylbutyramide (1256812-46-0)

Conditions	Yield
Stage #1: 4,4'-dicyano-4,4'-azo-di-valeric acid With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: Propargylamine In N,N-dimethyl-formamide at 0 - 25℃; for 12.5h; Inert atmosphere;	75%
With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Cooling with ice;	75%
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In dichloromethane for 3h;	69%
Stage #1: 4,4'-dicyano-4,4'-azo-di-valeric acid With 4-methyl-morpholine; isobutyl chloroformate In tetrahydrofuran at 20℃; for 0.333333h; Stage #2: Propargylamine In tetrahydrofuran at 20℃; for 4h;	48%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl (188526-94-5) → 4-cyano-4-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]pentanoic acid (1034133-00-0)

Conditions	Yield
In ethanol; water at 10℃; for 4h; UV-irradiation;	70%

3-azidopropan-1-ol (72320-38-8) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4,4'-azobis(3-azidopropyl 4-cyanopentanoate) (1280212-00-1)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran; dichloromethane at 4 - 20℃;	66%
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran; dichloromethane at 4 - 20℃;	1.5 g

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + 1-hydroxy-2-phenyl-2-(2',2',6',6'-tetramethyl-1'-piperidinyloxy)ethane (161776-41-6) → 4-Cyano-4-{1-cyano-1-methyl-3-[2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-ethoxycarbonyl]-propylazo}-4-methyl-butyric acid 2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-ethyl ester

Conditions	Yield
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃; for 72h;	65%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + 1-amino-3-(dimethylamino)propane (109-55-7) → DABPA

Conditions	Yield
Stage #1: 4,4'-dicyano-4,4'-azo-di-valeric acid With chloroformic acid ethyl ester; triethylamine In dichloromethane at -4℃; for 1.5h; Inert atmosphere; Stage #2: 1-amino-3-(dimethylamino)propane In dichloromethane at -4 - 20℃; for 24h; Inert atmosphere;	65%

N-BOC-1,2-diaminoethane (57260-73-8) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → (2-{4-[3-(2-tert-butoxycarbonylaminoethylcarbamoyl)-1-cyano-1-methylpropylazo]-4-cyano-4-methylbutyrylamino}-ethyl)carbamic acid tert-butyl ester (1426244-88-3)

Conditions	Yield
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In dichloromethane for 3h;	62%

t-butoxycarbonylhydrazine (870-46-2) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → N′-[4-cyano-4-(1-cyano-1-methyl-3-methylcarbamoylpropylazo)-4-methylbutyryl]hydrazinecarboxylic acid tert-butyl ester (1426244-85-0)

Conditions	Yield
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In dichloromethane for 3h;	61%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + allyl alcohol (107-18-6) → bisallyl 4,4'-azobis(4-cyanopentanoate) (124334-87-8)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; Darkness;	60%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + 1-aminooctadecane (124-30-1) → 4-cyano-4-(1-cyano-1-methyl-3-octadecylcarbamoyl-propylazo)-4-methyl-N-octadecyl-butyramide (939437-81-7)

Conditions	Yield
Stage #1: 4,4'-dicyano-4,4'-azo-di-valeric acid With dmap; triethylamine In dichloromethane for 0.25h; Stage #2: 1-aminooctadecane With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane for 18h; Further stages.;	59%
With dmap; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide; triethylamine In dichloromethane at 20℃; for 12h;	46%

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-cyano-4-(thiobenzoylthio)pentanoic acid (201611-92-9)

Conditions	Yield
With pyrrol-N-thiocarbonyl disulfides In ethyl acetate for 20h;	59%
Multi-step reaction with 3 steps 1: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 3 h / 20 °C 2: N-ethyl-N,N-diisopropylamine / dichloromethane / 20 °C / Inert atmosphere 3: ethyl acetate / 20 h / 80 °C / Inert atmosphere View Scheme

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + 2-hydroxyethyl acrylate (818-61-1) → C22H28N4O8

Conditions	Yield
Stage #1: 4,4'-dicyano-4,4'-azo-di-valeric acid With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane Stage #2: 2-hydroxyethyl acrylate In dichloromethane	54.1%

Upstream product

• 143-33-9 sodium cyanide 
• 123-76-2 levulinic acid 

Downstream Products

• 142599-94-8 C₁₂H₁₀Br₃N₂O₃ 
• 201611-92-9 4-cyano-4-(thiobenzoylthio)pentanoic acid 
• 5873-93-8 bis(thiobenzoyl) disulfide 
• 1351859-46-5 4-cyano-4-((2-phenylethylsulfanylthiocarbonyl)sulfanyl)pentanoic acid 
• 117431-67-1 C₁₂H₁₁Br₂N₂O₆S 
• 1451203-74-9 4-cyanopentanoic acid diselenobenzoate 
• 1160527-68-3 pentafluorophenyl 4-cyano-4-((phenylcarbonothioyl)thio)pentanoate 
• 1212057-35-6 N-biotinyl-N′-(3-(4-phenylthiocarbonylthio-4-cyanovaleryl)-3,6-dioxaoctane-1,8-diamine) 
• 1137725-46-2 cyano-4-[(ethylsulfanylthiocarbonyl)sulfanyl]-4-methylbutanoic acid 
• 864066-74-0 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid N-succinimidyl ester 

Relevant articles and documents

Oxidation of alkylcyanohydrazines to azo-bis nitriles using Oxone-potassium bromide in aqueous medium

Azo-bis nitriles were prepared in good yields and high purity by oxidation of corresponding 1,2-bis-dialkylcyano hydrazines using oxone-potassium bromide in aqueous medium.