4553-62-2

Basic information

• Product Name: 2-METHYLGLUTARONITRILE
• Synonyms: 2-METHYLGLUTARONITRILE;1,3-DICYANOBUTANE;METHYLGLUTARONITRILE;1,5-Valerodinitrile, 2-methyl-;2,4-Dicyanobutane;2-Methyl glutarodinitrile;2-Methyl pentanedinitrile;2-methyl-1,5-valerodinitrile
• CAS NO: 4553-62-2
• Molecular Formula: C₆H₈N₂
• Molecular Weight: 108.14
• EINECS: 224-923-5
• Product Categories: C6 to C7;Cyanides/Nitriles;Nitrogen Compounds
• Mol File: 4553-62-2.mol
• Article Data: 25

Chemical Properties

• Melting Point: −45 °C(lit.)
• Boiling Point: 269-271 °C(lit.)
• Flash Point: >230 °F
• Appearance: Clear liquid
• Density: 0.95 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0122mmHg at 25°C
• Refractive Index: n20/D 1.434(lit.)
• Storage Temp.: Store at +2°C to +8°C.
• Solubility: water: soluble
• Explosive Limit: 0.3-3.25%(V)
• Water Solubility: 52.3g/L at 20℃
• BRN: 1741955
• CAS DataBase Reference: 2-METHYLGLUTARONITRILE(CAS DataBase Reference)
• NIST Chemistry Reference: 2-METHYLGLUTARONITRILE(4553-62-2)
• EPA Substance Registry System: 2-METHYLGLUTARONITRILE(4553-62-2)

Safety Data

• Hazard Codes: Xn,T
• Statements: 20/21/22-23/25-21
• Safety Statements: 36/37-45-36/37/39
• RIDADR: 3276
• WGK Germany: 3
• RTECS: YV8140000
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 4553-62-2(Hazardous Substances Data)

Usage

Uses

2-Methylglutaronitrile (MGN) may be used in the synthesis of 1,5-dimethyl-2-piperidone (1,5-DMPD) by chemoenzymatic process.

General Description

Amber liquid.

Air & Water Reactions

Water soluble.

Reactivity Profile

Nitriles, such as 2-METHYLGLUTARONITRILE, 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.

Health Hazard

ACUTE/CHRONIC HAZARDS: 2-METHYLGLUTARONITRILE is readily absorbed through the skin.

Fire Hazard

2-METHYLGLUTARONITRILE is combustible.

InChI:InChI=1/C6H8N2/c1-6(5-8)3-2-4-7/h6H,2-3H2,1H3

Synthetic route

4-bromovalero-nitrile (14470-12-3) + tetra-n-butylammonium cyanide (10442-39-4) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With copper(l) iodide In acetonitrile at 20℃; for 24h; Inert atmosphere; UV-irradiation;	82%

hydrogen cyanide (74-90-8) + 3-pentenenitrile (4635-87-4) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With dicobalt octacarbonyl; benzene at 130℃;

1,3-dichlorobutane (1190-22-3) + sodium cyanide (143-33-9) → 4-chloro-valeronitrile (13249-56-4) + 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With 2-methoxy-ethanol at 160℃; unter Druck;
With 2-methoxy-ethanol at 159 - 163℃; under 1765.2 - 2059.4 Torr;

1,3-dibromobutane (107-80-2) + sodium cyanide (143-33-9) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With methanol

1,3-dibromobutane (107-80-2) + potassium cyanide (151-50-8) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With ethanol

4-chloro-valeronitrile (13249-56-4) + sodium cyanide (143-33-9) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With N,N-dimethyl-formamide

hydrogen cyanide (74-90-8) + buta-1,3-diene (106-99-0) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With dicobalt octacarbonyl; benzene at 130℃;

2-Methyl-glutaconsaeuredinitril (91808-25-2) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
palladium on activated charcoal (hydrogenation);

methanol (67-56-1) + carbon monoxide (201230-82-2) + acrylonitrile (107-13-1) → 2-methylglutaronitrile (4553-62-2) + 4,4-dimethoxybutanenitrile (14618-78-1) + propiononitrile (107-12-0)

Conditions	Yield
With dicobalt octacarbonyl; hydrogen In methanol at 100℃; under 129287 Torr; for 8h; Product distribution; Mechanism; var. catalysts, time and temp.;

carbon monoxide (201230-82-2) + acrylonitrile (107-13-1) + cyclohexanol (108-93-0) → 2-methylglutaronitrile (4553-62-2) + 3-Cyano-propionic acid cyclohexyl ester (125847-90-7) + Cyano-methyl-acetic acid cyclohexyl ester (125847-86-1) + 2,4-dicyano-2-methylbutanoic acid cyclohexyl ester (125847-81-6)

Conditions	Yield
With pyridine; dicobalt octacarbonyl In toluene at 110℃; under 75005.9 - 90007.2 Torr; for 6h;	A n/a B 5.3 % Chromat. C 28.9 % Chromat. D 61.7 % Chromat.

acrylonitrile (107-13-1) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
In N,N-dimethyl-formamide Rate constant; Mechanism; electrochemical hydrodimerization;

sulfuric acid (7664-93-9) + dihydrogen peroxide (7722-84-1) + iron(II) sulfate + propiononitrile (107-12-0) → meso-2,3-dimethyl-succinonitrile (55903-51-0) + hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
at 28℃;

2,4-dicyano-2-methyl-butyric acid → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
With pyridine; copper at 110℃;

1,3-dichlorobutane (1190-22-3) + sodium cyanide (143-33-9) + glycolmethyl ether → 4-chloro-valeronitrile (13249-56-4) + 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
at 159 - 163℃; unter Druck;

hydrogen cyanide (74-90-8) + 4-Pentenenitrile (592-51-8) → hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2) + alpha-ethylsuccinonitrile (17611-82-4)

Conditions	Yield
With {2-[(o-tolyl-O)2-P-O]-5-(1,1,3,3-Me4-butyl)benzene}2-SO2; Lewis acid; bis(1,5-cyclooctadiene)nickel (0) In N,N-dimethyl-formamide at 70℃; for 2h; sonication;

3-Pentenenitrile (16529-66-1) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2) + alpha-ethylsuccinonitrile (17611-82-4)

Conditions	Yield
With [BMMI][Tf2N]; tri-m-tolyl phosphite; zinc(II) chloride; bis(1,5-cyclooctadiene)nickel (0) at 70℃; for 3h; Product distribution; Further Variations:; Reagents; S;

hydrogen cyanide (74-90-8) + cis-2-pentenenitrile (25899-50-7) → hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2) + alpha-ethylsuccinonitrile (17611-82-4)

Conditions	Yield
With zinc(II) chloride In toluene at 50℃; for 16h; Conversion of starting material;
With iron(II) chloride; C54H64O6P2 In toluene at 50℃; for 6h; Conversion of starting material;
With iron(II) chloride In toluene at 25℃; for 72h; Conversion of starting material;

2-acetoxy-2-methyl-glutaronitrile (100377-27-3) → 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 500 °C 2: Pd-C / (hydrogenation) View Scheme

hydrogen cyanide (74-90-8) + cis-2-pentenenitrile (25899-50-7) + 2-pentenenitrile (26294-98-4) + 3-Pentenenitrile (16529-66-1) + tiglonitrile (30574-97-1) + 4-Pentenenitrile (592-51-8) + (Z)-pent-2-enenitrile (16545-78-1) → pentanonitrile (110-59-8) + hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2) + 4-ethenylcyclohexene (100-40-3)

Conditions	Yield
C48H52O4P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite; zinc(II) chloride Product distribution / selectivity;
C44H44O6P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite; zinc(II) chloride Product distribution / selectivity;

...Expand

(Z)-2-Butene (590-18-1) + hydrogen cyanide (74-90-8) + hexanedinitrile (111-69-3) + buta-1,3-diene (106-99-0) → cis-2-pentenenitrile (25899-50-7) + 2-pentenenitrile (26294-98-4) + 3-Pentenenitrile (16529-66-1) + (Z)-2-methyl-2-butenenitrile (20068-02-4) + tiglonitrile (30574-97-1) + 4-Pentenenitrile (592-51-8) + 2-METHYL-3-BUTENENITRILE (16529-56-9) + 2-methylglutaronitrile (4553-62-2) + 4-ethenylcyclohexene (100-40-3) + (Z)-pent-2-enenitrile (16545-78-1)

Conditions	Yield
Stage #1: (Z)-2-Butene; hydrogen cyanide; hexanedinitrile; buta-1,3-diene; C42H40O6P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite at 99.84℃; Stage #2: nickel at 109.84℃; Product distribution / selectivity;
C48H52O4P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite at 89.84℃; Product distribution / selectivity;

...Expand

(Z)-2-Butene (590-18-1) + hydrogen cyanide (74-90-8) + buta-1,3-diene (106-99-0) → 1-butylene (106-98-9) + cis-2-pentenenitrile (25899-50-7) + 2-pentenenitrile (26294-98-4) + 3-Pentenenitrile (16529-66-1) + (Z)-2-methyl-2-butenenitrile (20068-02-4) + tiglonitrile (30574-97-1) + 4-Pentenenitrile (592-51-8) + 2-METHYL-3-BUTENENITRILE (16529-56-9) + 2-methylglutaronitrile (4553-62-2) + 4-ethenylcyclohexene (100-40-3) + (Z)-pent-2-enenitrile (16545-78-1)

Conditions	Yield
Stage #1: (Z)-2-Butene; hydrogen cyanide; buta-1,3-diene; C48H52O4P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite at 83.84℃; Stage #2: at 119.84℃; Product distribution / selectivity;
Stage #1: (Z)-2-Butene; hydrogen cyanide; buta-1,3-diene; C42H40O6P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite at 89.84℃; Stage #2: zinc(II) chloride at 109.84℃; Product distribution / selectivity;
Stage #1: (Z)-2-Butene; hydrogen cyanide; buta-1,3-diene; C42H40O6P2; nickel(0)(cyclooctadienyl)2-complex at 89.84℃; Stage #2: C42H40O6P2; nickel(0)(cyclooctadienyl)2-complex at 109.84℃; Product distribution / selectivity;

...Expand

(Z)-2-Butene (590-18-1) + hydrogen cyanide (74-90-8) + buta-1,3-diene (106-99-0) → 1-butylene (106-98-9) + cis-2-pentenenitrile (25899-50-7) + 2-pentenenitrile (26294-98-4) + 3-Pentenenitrile (16529-66-1) + (Z)-2-methyl-2-butenenitrile (20068-02-4) + tiglonitrile (30574-97-1) + 4-Pentenenitrile (592-51-8) + 2-METHYL-3-BUTENENITRILE (16529-56-9) + 2-methylglutaronitrile (4553-62-2) + (Z)-pent-2-enenitrile (16545-78-1)

Conditions	Yield
C48H52O4P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite at 83.84℃; Product distribution / selectivity;
C44H44O6P2; nickel(0)(cyclooctadienyl)2-complex at 89.84℃; Product distribution / selectivity;
C44H44O6P2; nickel(0)(cyclooctadienyl)2-complex at 89.84℃; Product distribution / selectivity;
C48H52O4P2 at 83.84℃; Product distribution / selectivity;

...Expand

(Z)-2-Butene (590-18-1) + hydrogen cyanide (74-90-8) + buta-1,3-diene (106-99-0) → cis-2-pentenenitrile (25899-50-7) + 2-pentenenitrile (26294-98-4) + 3-Pentenenitrile (16529-66-1) + (Z)-2-methyl-2-butenenitrile (20068-02-4) + tiglonitrile (30574-97-1) + 4-Pentenenitrile (592-51-8) + 2-METHYL-3-BUTENENITRILE (16529-56-9) + 2-methylglutaronitrile (4553-62-2) + 4-ethenylcyclohexene (100-40-3) + (Z)-pent-2-enenitrile (16545-78-1)

Conditions	Yield
Stage #1: (Z)-2-Butene; hydrogen cyanide; buta-1,3-diene; C44H44O6P2; (m-tolyl-O-)(p-tolyl-O-)2P; (m-tolyl-O-)2(p-tolyl-O-)P; tri-m-tolyl phosphite; tri-p-tolylphosphite at 99.84℃; Stage #2: Lewis acid at 109.84℃; Product distribution / selectivity;

...Expand

hydrogen cyanide (74-90-8) → hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2)

Conditions	Yield
Stage #1: 3-pentenenitrile With zinc(II) chloride at 25 - 70℃; for 1.08333h; Stage #2: hydrogen cyanide at 70℃; for 2.5h; Product distribution / selectivity;
Stage #1: 3-pentenenitrile With zinc(II) chloride; C42H40O4P2; Ni(cod)2 at 25 - 40℃; for 1.08333h; Stage #2: hydrogen cyanide at 40℃; for 1.46667h; Product distribution / selectivity;
Stage #1: 3-pentenenitrile With zinc(II) chloride; C44H44O4P2; Ni(cod)2 at 25 - 40℃; for 1.08333h; Stage #2: hydrogen cyanide at 40℃; for 1.33333h; Product distribution / selectivity;
Stage #1: 3-pentenenitrile With zinc(II) chloride; C46H48O4P2; Ni(cod)2 at 25 - 40℃; for 1.08333h; Stage #2: hydrogen cyanide at 40℃; for 1.36667h; Product distribution / selectivity;
Stage #1: 3-pentenenitrile With zinc(II) chloride; C36H26O4P2; Ni(cod)2 at 25 - 70℃; for 1.08333h; Stage #2: hydrogen cyanide at 70℃; for 1h; Product distribution / selectivity;

3-pentenenitrile (4635-87-4) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → hexanedinitrile (111-69-3) + 2-methylglutaronitrile (4553-62-2) + alpha-ethylsuccinonitrile (17611-82-4)

Conditions	Yield
bis(1,5-cyclooctadiene)nickel (0); C68H92O6P2S; indium(III) trifluoroacetate at 70℃; for 3h; Conversion of starting material;
bis(1,5-cyclooctadiene)nickel (0); C56H68O12P2S; zinc(II) chloride at 70℃; for 3h; Conversion of starting material;
bis(1,5-cyclooctadiene)nickel (0); C68H68O8P2S; zinc(II) chloride at 70℃; for 3h; Conversion of starting material;

2-methylglutaronitrile (4553-62-2) → 2-methylglutaric acid (18069-17-5)

Conditions	Yield
With sulfuric acid; nitric acid at 90℃; for 16h; Reagent/catalyst; Temperature; Inert atmosphere;	96%
With hydrogenchloride
acid hydrolysis;
With sulfuric acid; water at 105 - 125℃; for 8.42h; Inert atmosphere;

2-methylglutaronitrile (4553-62-2) → 4-cyanopentanoic acid (23886-52-4)

Conditions	Yield
With potassium phosphate buffer; nitrilase from Alcaligenes faecalis ATCC8750 at 30℃; for 96h; pH=7.3;	91%
With glycerol for 72h; culture of Fusarium merismoides TG-1; Yield given;
With hydrogenchloride 1) microbial hydrolysis by Acidovorax facilis 72W, ATCC 55746; pH 7.0 (potassium phosphate buffer), 25 deg C, 21.5 h; 2) pH 2.5; Yield given. Multistep reaction;

2-methylglutaronitrile (4553-62-2) → 3-methylpiperidinehydrochloride (58531-29-6)

Conditions	Yield
Stage #1: 2-methylglutaronitrile With C46H178O41Si42; titanium(IV)isopropoxide In toluene at 100℃; for 24h; Inert atmosphere; Stage #2: With hydrogenchloride; water In toluene at 20℃; for 4h; Inert atmosphere; chemoselective reaction;	91%

2-methylglutaronitrile (4553-62-2) + 1,12-dodecanedioic acid (693-23-2) → 3-methyl-piperidine-2,6-dione (29553-51-3) + 1,12-dodecanedinitrile (4543-66-2)

Conditions	Yield
With aluminum (III) chloride at 200℃; for 5h;	A 88% B 81%

2-methylglutaronitrile (4553-62-2) → 2-methylglutaronitrile-d3

Conditions	Yield
With [carbonylchlorohydrido{bis[2-(diphenylphosphinomethyl)ethyl]amino}ethylamino] ruthenium(II); potassium tert-butylate; water-d2 at 70℃; for 24h; Inert atmosphere;	86%

Upstream product

• 74-90-8 hydrogen cyanide 
• 4635-87-4 3-pentenenitrile 
• 1190-22-3 1,3-dichlorobutane 
• 143-33-9 sodium cyanide 
• 107-80-2 1,3-dibromobutane 
• 151-50-8 potassium cyanide 
• 13249-56-4 4-chloro-valeronitrile 
• 106-99-0 buta-1,3-diene 
• 91808-25-2 2-Methyl-glutaconsaeuredinitril 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 107-13-1 acrylonitrile 
• 108-93-0 cyclohexanol 
• 7664-93-9 sulfuric acid 

Downstream Products

• 18545-83-0 diethyl 2-methylglutarate 
• 15520-10-2 2-methylcadaverine 
• 18069-17-5 2-methylglutaric acid 
• 23886-52-4 4-cyanopentanoic acid 
• 42856-62-2 2-methyl-1,5-pentanediol 
• 25899-50-7 cis-2-pentenenitrile 
• 26294-98-4 2-pentenenitrile 
• 16529-66-1 3-Pentenenitrile 
• 20068-02-4 (Z)-2-methyl-2-butenenitrile 
• 30574-97-1 tiglonitrile 
• 592-51-8 4-Pentenenitrile 
• 16529-56-9 2-METHYL-3-BUTENENITRILE 
• 100-40-3 4-ethenylcyclohexene 
• 16545-78-1 (Z)-pent-2-enenitrile 

Relevant articles and documents

Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source

An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.

METHOD FOR PRODUCING NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS

The present invention relates to a method for the hydrocyanation of organic ethylenically unsaturated compounds including at least one nitrile function. The invention specifically relates to a method for the hydrocyanation of a hydrocarbon compound including at least one ethylenic unsaturation by a reaction with hydrogen cyanide in a liquid medium and in the presence of a catalyst including a metal element selected from the transition metals and an organophosphorous ligand, the organophosphorous gaud including a compound of general formula (I), where R1 and R2, which are identical or different, are a linear or branched alkyl radical having 1-12 carbon atoms, which can include heteroatoms, or an optionally substituted aromatic or cycloaliphatic radical that can include heteroatoms, wherein the covalent bond between P and R1, and that between P and R2, are P—C bonds.

ORGANOPHOSPHORUS COMPOUNDS, CATALYTIC SYSTEMS COMPRISING SAID COMPOUNDS AND METHOD OF HYDROCYANATION USING SAID CATALYTIC SYSTEMS

The present invention relates to organophosphorus compounds belonging to the phosphinite-phosphite family, catalytic systems comprising a metallic element forming a complex with said phosphinite-phosphite compounds and methods of hydrocyanation employed in the presence of said catalytic systems.