4403-61-6

Basic information

• Product Name: 2-METHYL-2-BUTENENITRILE
• Synonyms: 2,3-DIMETHYLACRYLONITRILE;1-METHYL-1-PROPENYL CYANIDE;2-CYANO-2-BUTENE;2-METHYL-2-BUTENENITRILE;2-methyl-2-butenenitril;2-methyl-crotononitril;2-methylcrotononitrile;alpha,beta-dimethylacrylonitrile
• CAS NO: 4403-61-6
• Molecular Formula: C₅H₇N
• Molecular Weight: 81.12
• EINECS: 224-544-5
• Mol File: 4403-61-6.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 115-120 °C(lit.)
• Flash Point: -17 °C
• Appearance: clear liquid
• Density: 0.810 g/mL at 20 °C(lit.)
• Vapor Pressure: 13.2mmHg at 25°C
• Refractive Index: n20/D 1.417
• Water Solubility: Slightly soluble in water
• CAS DataBase Reference: 2-METHYL-2-BUTENENITRILE(CAS DataBase Reference)
• NIST Chemistry Reference: 2-METHYL-2-BUTENENITRILE(4403-61-6)
• EPA Substance Registry System: 2-METHYL-2-BUTENENITRILE(4403-61-6)

Safety Data

• Hazard Codes: F,Xn
• Statements: 11-20/22
• Safety Statements: 16-23-36/37
• RIDADR: UN 3273 3/PG 2
• WGK Germany: 3
• RTECS: EM8312500
• HazardClass: 3.1
• PackingGroup: I
• Hazardous Substances Data: 4403-61-6(Hazardous Substances Data)

Usage

Air & Water Reactions

Highly flammable. 2-METHYL-2-BUTENENITRILE may be sensitive to prolonged exposure to air. . Insoluble in water.

Reactivity Profile

Nitriles, such as 2-METHYL-2-BUTENENITRILE, may polymerize in the presence of metals and some metal compounds. They are incompatible with acids; mixing nitriles with strong oxidizing acids can lead to extremely violent reactions. Nitriles are generally incompatible with other oxidizing agents such as peroxides and epoxides. The combination of bases and nitriles can produce hydrogen cyanide. Nitriles are hydrolyzed in both aqueous acid and base to give carboxylic acids (or salts of carboxylic acids). These reactions generate heat. Peroxides convert nitriles to amides. Nitriles can react vigorously with reducing agents. Acetonitrile and propionitrile are soluble in water, but nitriles higher than propionitrile have low aqueous solubility. They are also insoluble in aqueous acids.

Fire Hazard

2-METHYL-2-BUTENENITRILE is flammable.

InChI:InChI=1/C5H7N/c1-3-5(2)4-6/h3H,1-2H3

Synthetic route

2-METHYL-3-BUTENENITRILE (16529-56-9) → 2-methyl-2-butene nitrile (4403-61-6)

Conditions	Yield
With aluminum oxide at 85℃; for 18h;	98%
recovered isomerization catalyst at 120℃; for 5h; Conversion of starting material;

dimethylacetylene (503-17-3) + 2-vinylbenzonitrile (34560-28-6) → 2-methyl-2-butene nitrile (4403-61-6) + 2,3-dimethyl-1-methylene-1H-indene

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); dimethylaluminum chloride; triphenylphosphine In hexane; toluene at 60℃; for 16h; Inert atmosphere; Glovebox;	A n/a B 67%

3-Ethylsulfanyl-2-methyl-butyronitrile (108671-31-4) → 2-methyl-2-butene nitrile (4403-61-6)

Conditions	Yield
With tetrabutylammomium bromide In methanol electrolysis;	28%

2-hydroxy-2-methyl-butyronitrile (4111-08-4) → 2-methyl-2-butene nitrile (4403-61-6)

Conditions	Yield
With phosphorus pentaoxide α.β-dimethyl-acrylic acid nitrile;
With phosphorus pentachloride α.β-dimethyl-acrylic acid nitrile;

(Z)-2-Butene (590-18-1) + ethanedinitrile (460-19-5) → (Z)-2-butenenitrile (1190-76-7) + crotononitrile (4786-20-3) + 2-methyl-2-butene nitrile (4403-61-6) + ethane (74-84-0) + but-3-enenitrile (109-75-1) + methacrylonitrile (126-98-7)

Conditions	Yield
Product distribution; Mechanism; Irradiation; power, flow rates dependence;

Reaxys ID: 11463818 → 2-methyl-2-butene nitrile (4403-61-6) + 4-Pentenenitrile (592-51-8) + 3-pentenenitrile (4635-87-4)

Conditions	Yield
bis(cyclooctadiene-1,5)nikel; trifuran-2-yl-phosphane at 100℃; for 1h; Product distribution / selectivity;
bis(cyclooctadiene-1,5)nikel; diphenyl(2-furyl)phosphane at 100℃; for 1h; Product distribution / selectivity;
bis(cyclooctadiene-1,5)nikel; 2,2'-(phenylphosphiniden)bisfuran at 100℃; for 1h; Product distribution / selectivity;

2-METHYL-3-BUTENENITRILE (16529-56-9) → 2-methyl-2-butene nitrile (4403-61-6) + 3-pentenenitrile (4635-87-4)

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); 1,4-di(diphenylphosphino)-butane In toluene at 100℃; Catalytic behavior; Reagent/catalyst; Schlenk technique; Inert atmosphere;

hydrogen cyanide (74-90-8) + buta-1,3-diene (106-99-0) → 2-methyl-2-butene nitrile (4403-61-6)

Conditions	Yield
Stage #1: hydrogen cyanide; buta-1,3-diene Stage #2: With calcium hydroxide at 140℃; under 750.075 Torr; for 8h; Reagent/catalyst; Temperature;

methyl aminal ester + 2-methyl-2-butene nitrile (4403-61-6) → 2-chloro-5-methylpyridine (18368-64-4)

Conditions	Yield
In water; acetic acid; toluene	98.6%

2-methyl-2-butene nitrile (4403-61-6) + benzoic acid anhydride (93-97-0) → 2-benzoyl-2-methylbutanenitrile (80589-05-5)

Conditions	Yield
With HRu(1,3-bis(6'-methyl-2'-pyridylimino)isoindoline)(PPh3)2; hydrogen; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 100℃; under 5931.67 Torr; for 15h; Sealed tube;	81%

2-methyl-2-butene nitrile (4403-61-6) + N-Phenylhydroxylamine (100-65-2) → 2-methylene-3-(phenylamino)butanenitrile (1392285-97-0)

Conditions	Yield
With iron(II) chloride tetrahydrate In 1,4-dioxane at 70℃; for 6h;	42%

2-methyl-2-butene nitrile (4403-61-6) + benzhydrylidene(methyl)amine (552-82-9) → C18H20N2 (1359859-58-7)

Conditions	Yield
With BF4(1-)*C40H40IrN4(1+) In 1-methyl-pyrrolidin-2-one at 25℃; for 18h; Inert atmosphere; Irradiation;	32%

2-methyl-2-butene nitrile (4403-61-6) → 4-Chloro-3-methylbenzaldehyde (101349-71-7)

Conditions	Yield
With trichlorophosphate In N,N-dimethyl-formamide at 110℃; for 24h;	21%

2-methyl-2-butene nitrile (4403-61-6) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 6-chloro-5-methylpyridine-3-carboxaldehyde (176433-43-5)

Conditions	Yield
With trichlorophosphate at 90 - 110℃; for 15h; Inert atmosphere;	20%
With trichlorophosphate at 100 - 110℃; for 15h; Inert atmosphere;	15%
Stage #1: 2-methyl-2-butene nitrile; N,N-dimethyl-formamide With trichlorophosphate at 90 - 110℃; for 15h; Stage #2: With water In dichloromethane at 0℃;

2-methyl-2-butene nitrile (4403-61-6) → 2-Methylbutylamine (96-15-1)

Conditions	Yield
With acetic anhydride; platinum Hydrogenation.Erwaermen des Reaktionsprodukts mit wss.-aethanol.Natronlauge;

2-methyl-2-butene nitrile (4403-61-6) + trimethylsilan (993-07-7) → N,N-Bis--2-methyl-butylamin (18107-23-8) + 1,1,1,3,3,3-Hexamethyl-2-((Z)-2-methyl-but-2-enyl)-disilazane (124582-78-1) + (Z)-1,1,1-trimethyl-N-(2-methyl-1-butenyl)-N-(trimethylsilyl)silanamine (124582-76-9) + (E)-1,1,1-trimethyl-N-(2-methyl-1-butenyl)-N-(trimethylsilyl)silanamine (124582-77-0)

Conditions	Yield
dicobalt octacarbonyl In toluene at 60℃; for 20h; CO atmosphere; Yield given. Further byproducts given. Yields of byproduct given. Title compound not separated from byproducts;

2-methyl-2-butene nitrile (4403-61-6) + trimethylsilan (993-07-7) → 1,1,1,3,3,3-Hexamethyl-2-((Z)-2-methyl-but-2-enyl)-disilazane (124582-78-1) + 1,1,1,3,3,3-Hexamethyl-2-((E)-2-methyl-but-2-enyl)-disilazane (124582-79-2) + (Z)-1,1,1-trimethyl-N-(2-methyl-1-butenyl)-N-(trimethylsilyl)silanamine (124582-76-9) + (E)-1,1,1-trimethyl-N-(2-methyl-1-butenyl)-N-(trimethylsilyl)silanamine (124582-77-0)

Conditions	Yield
dicobalt octacarbonyl In toluene at 60℃; for 20h; CO atmosphere; Yield given. Further byproducts given. Yields of byproduct given. Title compound not separated from byproducts;

2-methyl-2-butene nitrile (4403-61-6) + trimethylsilyl iodide (16029-98-4) → 2-methyl-4-trimethylsilyl-2-butenenitrile + 2-methyl-4-trimethylsilyl-2-butenenitrile

Conditions	Yield
With triethylamine at 120℃; for 10h; Yield given. Yields of byproduct given;

2-methyl-2-butene nitrile (4403-61-6) + ethyl diethoxymethylphosphinate (65600-74-0) → (2-Cyano-1,2-dimethyl-ethyl)-diethoxymethyl-phosphinic acid ethyl ester

Conditions	Yield
With sodium ethanolate In ethanol

2-methyl-2-butene nitrile (4403-61-6) → Tiglic acid (80-59-1) + (Z)-2-methyl-2-butenenitrile (20068-02-4)

Conditions	Yield
With Escherichia coli SS1001 cells immobilized in alginate beads In water at 35℃; for 22h;	A 13.2 g B n/a

2-methyl-2-butene nitrile (4403-61-6) → (Z)-2-methyl-2-buteneamide (5953-75-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: Escherichia coli SS1001 cells immobilized in alginate beads / H2O / 22 h / 35 °C 2: 27 percent Chromat. / Comamonas testosteroni 5-MGAM-4D; potassium phosphate buffer / H2O / 0.25 h / 25 °C View Scheme

2-methyl-2-butene nitrile (4403-61-6) → (3-Amino-1,2-dimethyl-propyl)-phosphinic acid

Conditions	Yield
Multi-step reaction with 3 steps 1: NaOEt / ethanol 2: H2, NH3 / Ni / ethanol 3: HCl, propylene oxide / Heating View Scheme

2-methyl-2-butene nitrile (4403-61-6) → (3-Amino-1,2-dimethyl-propyl)-diethoxymethyl-phosphinic acid ethyl ester

Conditions	Yield
Multi-step reaction with 2 steps 1: NaOEt / ethanol 2: H2, NH3 / Ni / ethanol View Scheme

2-pentenenitrile (13284-42-9) + 2-methyl-2-butene nitrile (4403-61-6) + 2-METHYL-3-BUTENENITRILE (16529-56-9) + 3-pentenenitrile (4635-87-4) → 4-Pentenenitrile (592-51-8)

Conditions	Yield
Stage #1: 2-pentenenitrile; 2-methyl-2-butene nitrile; 2-METHYL-3-BUTENENITRILE; 3-pentenenitrile With 1-butyl-3-methylimidazolium trifluoromethanesulfonimide; bis(1,5-cyclooctadiene)nickel (0); sodium triphenylphosphate at 20℃; for 0.166667h; Stage #2: In n-heptane at 100℃; for 3h; Product distribution / selectivity;
With 1-butyl-2,3-dimethylimidazolium bis-(trifluoromethanesulfonyl)amide; bis(1,5-cyclooctadiene)nickel (0); sodium triphenylphosphate at 100℃; for 3h; Product distribution / selectivity;
With 1-butyl-3-methylimidazolium trifluoromethanesulfonimide; bis(1,5-cyclooctadiene)nickel (0); sodium triphenylphosphate at 100℃; for 3h; Product distribution / selectivity;

2-methyl-2-butene nitrile (4403-61-6) → Tiglic acid (80-59-1)

Conditions	Yield
With water; Alginate-immobilized E. coli SS1001 Cells at 35℃; for 18 - 22h; pH=7.0; Product distribution / selectivity; Enzymatic reaction; calcium acetate buffer;	99 - 100 %Chromat.
With water; alginate-immobilized A. facilis 72W cells at 35℃; for 18 - 20h; pH=7.0; Conversion of starting material; Enzymatic reaction; calcium acetate buffer;	97 - 100 %Chromat.
With water; alginate-immobilized E. coli SS1001 cells at 35℃; for 20h; pH=7.0; Conversion of starting material; Enzymatic reaction; Aqueous acetate buffer;	97 - 100 %Chromat.
With water; carrageenan-immobilized E. coli SS1001 cells at 35℃; for 18 - 20h; Conversion of starting material; Enzymatic reaction;	96 %Chromat.

2-methyl-2-butene nitrile (4403-61-6) → Tiglic acid (80-59-1) + (Z)-2-methyl-2-buteneamide (5953-75-3)

Conditions	Yield
With water; C. Testosteroni S2B-1 Cells at 25℃; for 21 - 47h; pH=7.0; Product distribution / selectivity; Enzymatic reaction; potassium phosphate buffer;	A 89 - 100 %Chromat. B 1.2 - 87 %Chromat.

2-methyl-2-butene nitrile (4403-61-6) → 6-chloro-5-methylpyridine-3-carboxaldehyde (176433-43-5)

Conditions	Yield
With trichlorophosphate In N,N-dimethyl-formamide at 90 - 110℃; for 15h;

2-methyl-2-butene nitrile (4403-61-6) → 6-chloro-5-methylnicotinic acid ethyl ester (942511-70-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: trichlorophosphate / 90 - 110 °C 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C 3: sulfuric acid / 48 h / Reflux View Scheme
Multi-step reaction with 3 steps 1: trichlorophosphate / 15 h / 90 - 110 °C / Inert atmosphere 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C 3: sulfuric acid / 48 h / Inert atmosphere; Reflux View Scheme
Multi-step reaction with 3 steps 1.1: trichlorophosphate / 15 h / 90 - 110 °C 1.2: 0 °C 2.1: formic acid; dihydrogen peroxide / water / 15 h / 0 °C 3.1: sulfuric acid / 48 h / Heating / reflux View Scheme
Multi-step reaction with 3 steps 1: trichlorophosphate / 90 - 110 °C 2: dihydrogen peroxide / formic acid; water / 15 h / 0 °C 3: sulfuric acid / 48 h / Reflux View Scheme

2-methyl-2-butene nitrile (4403-61-6) → 6-chloro-5-methylpyridin-3-ylcarboxylic acid (66909-29-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: trichlorophosphate / 90 - 110 °C 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C View Scheme
Multi-step reaction with 2 steps 1: trichlorophosphate / 15 h / 90 - 110 °C / Inert atmosphere 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C View Scheme
Multi-step reaction with 2 steps 1.1: trichlorophosphate / 15 h / 90 - 110 °C 1.2: 0 °C 2.1: formic acid; dihydrogen peroxide / water / 15 h / 0 °C View Scheme
Multi-step reaction with 2 steps 1: trichlorophosphate / 90 - 110 °C 2: dihydrogen peroxide / formic acid; water / 15 h / 0 °C View Scheme

2-methyl-2-butene nitrile (4403-61-6) → isopropyl 6-chloro-5-methylnicotinate (1122090-09-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: trichlorophosphate / 90 - 110 °C 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C 3: chloro-trimethyl-silane / 18 h / 70 °C View Scheme
Multi-step reaction with 3 steps 1: trichlorophosphate / 15 h / 90 - 110 °C / Inert atmosphere 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C 3: chloro-trimethyl-silane / 18 h / 80 °C / Inert atmosphere View Scheme

2-methyl-2-butene nitrile (4403-61-6) → isopropyl 6-cyclopentyl-5-methylnicotinate (1122090-11-2)

Conditions	Yield
Multi-step reaction with 4 steps 1: trichlorophosphate / 90 - 110 °C 2: formic acid; dihydrogen peroxide / water / 15 h / 0 °C 3: chloro-trimethyl-silane / 18 h / 70 °C 4: Pd(dppf) / 1,4-dioxane; tetrahydrofuran / 18 h / 75 °C / Inert atmosphere View Scheme

Upstream product

• 4111-08-4 2-hydroxy-2-methyl-butyronitrile 
• 16529-56-9 2-METHYL-3-BUTENENITRILE 
• 74-90-8 hydrogen cyanide 
• 106-99-0 buta-1,3-diene 
• 503-17-3 dimethylacetylene 
• 34560-28-6 2-vinylbenzonitrile 
• 108671-31-4 3-Ethylsulfanyl-2-methyl-butyronitrile 
• 590-18-1 (Z)-2-Butene 
• 460-19-5 ethanedinitrile 

Downstream Products

• 96-15-1 2-Methylbutylamine 
• 80-59-1 Tiglic acid 
• 20068-02-4 (Z)-2-methyl-2-butenenitrile 
• 176433-43-5 6-chloro-5-methylpyridine-3-carboxaldehyde 
• 592-51-8 4-Pentenenitrile 
• 4635-87-4 3-pentenenitrile 
• 80589-05-5 2-benzoyl-2-methylbutanenitrile 
• 101349-71-7 4-Chloro-3-methylbenzaldehyde 
• 150807-88-8 2-chloro-3-methyl-5-pyridylmethyl chloride 
• 887707-21-3 (6-chloro-5-methylpyridin-3-yl)methanol 
• 1186617-39-9 5-methyl-6-pyrrolidin-1-yl-nicotinic acid 
• 1186618-27-8 C₂₄H₃₁N₅O₃ 
• 1186617-62-8 2-ethyl-6-methyl-4-[5-(5-methyl-6-pyrrolidin-1-yl-pyridin-3-yl)-[1,2,4]oxadiazol-3-yl]-phenol 
• 1186618-30-3 N-((S)-3-{2-ethyl-6-methyl-4-[5-(5-methyl-6-pyrrolidin-1-yl-pyridin-3-yl)-[1,2,4]oxadiazol-3-yl]phenoxy}-2-hydroxypropyl)-2-hydroxyacetamide 

Relevant articles and documents

Theoretical and experimental study of the nickel-catalyzed isomerization of 2-Methyl-3-butenenitrile and the effect of a Lewis acid

A combined experimental and theoretical study was conducted to investigate the isomerization of 2-methyl-3-butenenitrile (2M3BN) to 3-pentenenitrile (3PN) and to 2-methyl-2-butenenitrile (2M2BN) catalyzed by nickel diphosphine complexes. Ni(1,4-bis(diphenylphosphino)butane) (dppb) was identified as the most reactive catalyst among the complexes that we examined experimentally. Quantum mechanics (density functional theory) was then used to study the two isomerization mechanisms catalyzed by this complex. We find that for the 2M3BN?→?3PN isomerization, the reaction is initiated with [Formula presented] bond cleavage, followed by an allyl direct rotation and [Formula presented] bond reformation. For the 2M3BN?→?2M2BN isomerization, the most energetically favorable pathway begins with [Formula presented] bond activation, followed by a π-σ-σ-π allyl rearrangement and [Formula presented] bond reformation. Our proposed mechanism for the 2M3BN?→?2M2BN isomerization is slightly different (yet energetically more favorable) than that described in previous studies, where it has been suggested that 2M2BN is obtained through a π-σ-σ allyl rearrangement rather than a π-σ-σ-π type rearrangement. Additionally, we investigated the effect of Lewis acids in the 2M3BN?→?3PN isomerization, which has been shown in most experiments to attenuate the reaction. Notably, our calculations indicated that ZnCl2, which is used as a model Lewis acid, actually reduces the barriers for all elementary steps. However, the effective kinetic barrier for the isomerization increases from 23.7 (without ZnCl2) to 24.0?kcal/mol because of the formation of a very stable Ni(π-allyl) ([Formula presented]2) intermediate, causing a decrease in the reaction rate. This theoretical result was further confirmed by our own experiments.

Unlocking Mizoroki–Heck-Type Reactions of Aryl Cyanides Using Transfer Hydrocyanation as a Turnover-Enabling Step

A new transfer hydrofunctionalization strategy to turnover H-MII-X complexes has enabled both intra- and intermolecular Mizoroki–Heck (MH)-type reactions of aryl cyanides that are challenging to realize under traditional, basic conditions. Initially, a cascade carbonickelation/MH reaction of 2-cyanostyrenes was achieved using a key alkyne transfer hydrocyanation step. Mechanistic experiments supported the proposed catalytic cycle, including the turnover-enabling transfer hydrocyanation step. The reactivity was then extended to the intermolecular MH reaction of benzonitriles and styrenes.

Method for making nitrile compounds from ethylenically unsaturated compounds

The invention concerns a method for hydrocyanation of ethylenically unsaturated organic compounds comprising at least a nitrile function. The invention provides a method for hydrocyanation of an ethylenically unsaturated hydrocarbon compound by reacting in liquid medium the hydrogen cyanide in the presence of a catalyst comprising a metal element selected among transition metals and an organophosphorous ligand, characterised in that the organophosphorous ligand is a furylphosphine. The invention is in particular useful for synthesizing adiponitrile from butadiene.