2-Methylglutaronitrile

Last updated
2-Methylglutaronitrile
2-Methylglutaronitril Struktur.svg
Names
Preferred IUPAC name
2-Methylpentanedinitrile
Other names
1,3-Dicyanobutane, α-Methylvalerodinitrile
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.022.658 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 224-923-5
MeSH C480967
PubChem CID
UNII
  • InChI=1S/C6H8N2/c1-6(5-8)3-2-4-7/h6H,2-3H2,1H3
    Key: FPPLREPCQJZDAQ-UHFFFAOYSA-N
  • CC(CCC#N)C#N
Properties
C6H8N2
Molar mass 108.144 g·mol−1
Appearancecolorless liquid
Density 0.9548 g/cm3
Melting point −45 °C (−49 °F; 228 K)
Boiling point 263 °C (505 °F; 536 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

2-Methylglutaronitrile is the organic compound with the formula NCCH2CH2CH(CH3)CN. This dinitrile is obtained in the large-scale synthesis of adiponitrile. It is a colorless liquid with an unpleasant odor. It is the starting compound for the vitamin nicotinamide and for the diester dimethyl-2-methylglutarate and the ester amide methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, which are promoted as green solvents. 2-Methylglutaronitrile is chiral but is mainly encountered as the racemate. It is also used to make Dytek A. [1]

Contents

Occurrence and production

2-Methylglutaronitrile is a by-product of the production of adiponitrile, the precursor of hexamethylenediamine and adipic acid as building blocks for nylon 66.

Starting from 1,3-butadiene or a butadiene-rich C4-section (> 40% by volume) from a naphtha steamcracker in the first stage a mixture of pentenenitriles is obtained through hydrocyanation (using as catalyst Ni0-phosphine [PR3] [2] or phosphite or phosphonite [P(OR)2R] [3] ). The mixture contains mainly trans-3-pentenenitrile in addition to the isomers 2-methyl-2-butenenitrile, 4-pentenenitrile and 2-pentenenitrile.

1,3-Butsdien zu Pentennitrilen Pentennitrile durch Hydrocyanierung von Butadien.svg
1,3-Butsdien zu Pentennitrilen

The mixture of monoolefinic C5 mononitriles is isomerized to 3- and 4-pentenenitrile with a hydrocyanation catalyst and a Lewis acid (such as ZnCl2). [3] In the third step, the mixture is reacted with hydrogen cyanide to give a mixture of dinitriles which contains in addition to 2-methylglutaronitrile also adiponitrile and 2-ethylbutanedinitrile.

Umsetzung von Pentennitrilen zu Dinitrilen Dinitrile aus Pentennitrilen.svg
Umsetzung von Pentennitrilen zu Dinitrilen

2-Methylglutaronitrile can be separated by fractional distillation. [4]

The 2-methylglutaronitrile-rich fraction has hitherto been combusted as an undesired by-product of adiponitrile production, having the typical composition of about 86 wt% 2-methylglutaronitrile, 11 wt% 2-succinonitrile and 3 wt% adiponitrile. [5] [6]

Applications

2-methylglutaronitrile can be converted to 3-methylpyridine (β-picoline) by partial hydrogenation. [7] [8]

3-Methylpyridin aus 2-MGN 2-MGN zu 3-Methylpyiridin.svg
3-Methylpyridin aus 2-MGN

In addition to 3-methylpyridine, 3-methylpiperidine is obtained as a by-product from which further 3-methylpyridine can be obtained by dehydrogenation.

Ammonoxidation of 3-methylpyridine on transition metal contacts yields 3-cyanopyridine (nicotinonitrile) in yields of 95%. [9]

Nicotinsaureamid aus 3-Methylpyridin 3-Methylpyridin zu Nicotinsaureamid.svg
Nicotinsäureamid aus 3-Methylpyridin

Hydrogenation of a solution of 2-methylglutaronitrile in ethanol in the presence of Raney cobalt at 15 bar and 100 °C yields 2-methylpentane-1,5-diamine. [10]

2-Methylpentan-1,5-diamin aus 2-Methylglutaronitril 2-MGN zu 2-Methylpentan-1,5-diamin.svg
2-Methylpentan-1,5-diamin aus 2-Methylglutaronitril

2-Methylpentanediamine can be converted to 3-methylpiperidine at 300 to 400 °C on a zeolite contact and then dehydrated on a palladium contact to 3-methylpyridine, which can be converted via nicotinonitrile into nicotinamide. [11]

The racemic diamine can also be used for the preparation of specific polyamides and after reaction with phosgene to form 2-methylpentane diisocyanate [12] as a reaction component in polyurethanes. Nitrilases regioselectively hydrolyze the ω-nitrile group in α, ω-dinitriles without detectable amide intermediate directly to the carboxyl group. 4-cyanopentanoic acid is formed in high yield. [13]

4-Cyanopentansaure aus 2-Methylglutaronitril 2-MGN zu 4-Cyanopentansaure.svg
4-Cyanopentansäure aus 2-Methylglutaronitril

The ammonium salt of 4-cyanopentanoic acid can be converted by catalytic hydrogenation in the presence of methylamine in 1,5-dimethyl-2-piperidone, [14] [15] an environmentally compatible solvent. [16]

Synthese von 1,5-Dimethyl-2-piperidon 1,5-Dimethyl-2-piperidon-Synthese.svg
Synthese von 1,5-Dimethyl-2-piperidon

The hydrolysis of both nitrile groups of 2-methylglutaronitrile with e.g. 20% sodium hydroxide solution at 50 °C and subsequent acidification produces 2-methylglutaric acid. [17]

2-Methylglutarsaure aus 2-Methylglutraronitril 2-MGN zu 2-Methylglutarsaure.svg
2-Methylglutarsäure aus 2-Methylglutraronitril

Starting from 2-methylglutaronitrile the hydrolysis to 2-methylglutaric acid can also be accomplished via the 2-methylglutarimide obtained by heating a 2-methylglutaronitrile/water mixture to 275 °C in the presence of a titanium dioxide catalyst in yields of 94%. [18]

2-MGN-Imid aus 2-Methylglutaronitril 2-MGN zu 2-MGN-Imid.svg
2-MGN-Imid aus 2-Methylglutaronitril

Hydrolysis in the alkaline provides 2-methyl glutaric acid.

The reaction of 2-methylglutarimide with e.g. methanol (methanolysis) produces the diester dimethyl-2-methylglutarate [19] in the presence of titanium dioxide [5] or lanthanum oxide. [20] It was commercialized as an environmentally friendly aprotic dipolar solvent under the name Rhodiasolv IRIS with the typical composition 87-89% dimethyl-2-methylglutarate, 9-11% dimethyl 2-ethylbutanedioate and 1-2% dimethyl hexanedioate [6] as a substitute for acetone, dichloromethane, N-methylpyrrolidone and the like.

Diester aus 2-MGN-Imid 2-MGN-Imid zu Diester.svg
Diester aus 2-MGN-Imid

The ester mixture is very similar to so-called dibasic esters, which are commercially available as FlexiSolv DBE esters. [21]

The diester can be selectively converted into a mixture of 1- or 5-substituted methyl ester amides with dimethylamine in methanol/sodium methoxide, [22] which is used under the name Rhodiasolv Polarclean as formulation auxiliaries for crop protection preparations. [6] The resulting ester amides are readily biodegradable and good solvents for a variety of different plant protection agents (such as insecticides or fungicides), also compared to the frequently used N-methylpyrrolidone, cyclohexanone or isophorone.

Other esteramides are derived, e. g. from 2-methylglutaronitrile which, after alkaline hydrolysis, is converted into 2-methylglutaric acid, cyclized with acetic anhydride to give 2-methylglutaric anhydride, reacted with dimethylamine to form the monoamide, reacted to an acid chloride with thionyl chloride and formed to an ester with more hydrophobic alcohols (like butanols or cyclohexanol). [23]

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

Transesterification is the process of exchanging the organic functional group R″ of an ester with the organic group R' of an alcohol. These reactions are often catalyzed by the addition of an acid or base catalyst. Strong acids catalyze the reaction by donating a proton to the carbonyl group, thus making it a more potent electrophile. Bases catalyze the reaction by removing a proton from the alcohol, thus making it more nucleophilic. The reaction can also be accomplished with the help of other enzymes, particularly lipases.

<span class="mw-page-title-main">Malonic acid</span> Carboxylic acid with chemical formula CH2(COOH)2

Malonic acid (IUPAC systematic name: propanedioic acid) is a dicarboxylic acid with structure CH2(COOH)2. The ionized form of malonic acid, as well as its esters and salts, are known as malonates. For example, diethyl malonate is malonic acid's diethyl ester. The name originates from the Greek word μᾶλον (malon) meaning 'apple'.

In organic chemistry, a nitrile is any organic compound that has a −C≡N functional group. The name of the compound is composed of a base, which includes the carbon of the −C≡N, suffixed with "nitrile", so for example CH3CH2C≡N is called "propionitrile". The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

In organic chemistry, hydrocyanation is a process for conversion of alkenes to nitriles. The reaction involves the addition of hydrogen cyanide and requires a catalyst. This conversion is conducted on an industrial scale for the production of precursors to nylon.

<span class="mw-page-title-main">Dimethyl terephthalate</span> Chemical compound

Dimethyl terephthalate (DMT) is an organic compound with the formula C6H4(COOCH3)2. It is the diester formed from terephthalic acid and methanol. It is a white solid that melts to give a distillable colourless liquid.

<span class="mw-page-title-main">Glutaric acid</span> Chemical compound

Glutaric acid is the organic compound with the formula C3H6(COOH)2. Although the related "linear" dicarboxylic acids adipic and succinic acids are water-soluble only to a few percent at room temperature, the water-solubility of glutaric acid is over 50% (w/w).

<span class="mw-page-title-main">Adiponitrile</span> Chemical compound

Adiponitrile is an organic compound with the chemical formula (CH2)4(CN)2. This viscous, colourless dinitrile is an important precursor to the polymer nylon 66. In 2005, about one million tonnes of adiponitrile were produced.

<span class="mw-page-title-main">Carbonate ester</span> Chemical group (R–O–C(=O)–O–R)

In organic chemistry, a carbonate ester is an ester of carbonic acid. This functional group consists of a carbonyl group flanked by two alkoxy groups. The general structure of these carbonates is R−O−C(=O)−O−R' and they are related to esters, ethers and also to the inorganic carbonates.

<span class="mw-page-title-main">Dimethyl oxalate</span> Chemical compound

Dimethyl oxalate is an organic compound with the formula (CO2CH3)2. It is the dimethyl ester of oxalic acid. Dimethyl oxalate is a colorless or white solid that is soluble in water.

<span class="mw-page-title-main">Diethylaluminium cyanide</span> Chemical compound

Diethylaluminium cyanide is the organoaluminium compound with formula ( 2AlCN)n. This colorless compound is usually handled as a solution in toluene. It is a reagent for the hydrocyanation of α,β-unsaturated ketones.

The Chichibabin pyridine synthesis is a method for synthesizing pyridine rings. The reaction involves the condensation reaction of aldehydes, ketones, α,β-Unsaturated carbonyl compounds, or any combination of the above, with ammonia. It was reported by Aleksei Chichibabin in 1924. Methyl-substituted pyridines, which show widespread uses among multiple fields of applied chemistry, are prepared by this methodology.

Oleochemistry is the study of vegetable oils and animal oils and fats, and oleochemicals derived from these fats and oils. The resulting product can be called oleochemicals (from Latin: oleum "olive oil"). The major product of this industry is soap, approximately 8.9×106 tons of which were produced in 1990. Other major oleochemicals include fatty acids, fatty acid methyl esters, fatty alcohols and fatty amines. Glycerol is a side product of all of these processes. Intermediate chemical substances produced from these basic oleochemical substances include alcohol ethoxylates, alcohol sulfates, alcohol ether sulfates, quaternary ammonium salts, monoacylglycerols (MAG), diacylglycerols (DAG), structured triacylglycerols (TAG), sugar esters, and other oleochemical products.

<span class="mw-page-title-main">Cyclohexanedimethanol</span> Chemical compound

Cyclohexanedimethanol (CHDM) is a mixture of isomeric organic compounds with formula C6H10(CH2OH)2. It is a colorless low-melting solid used in the production of polyester resins. Commercial samples consist of a mixture of cis and trans isomers. It is a di-substituted derivative of cyclohexane and is classified as a diol, meaning that it has two OH functional groups. Commercial CHDM typically has a cis/trans ratio of 30:70.

11-Aminoundecanoic acid is an organic compound with the formula H2N(CH2)10CO2H. This white solid is classified as an amine and a fatty acid. 11-Aminoundecanoic acid is a precursor to Nylon-11.

<span class="mw-page-title-main">2-Ethyl-2-oxazoline</span> Chemical compound

2-Ethyl-2-oxazoline (EtOx) is an oxazoline which is used particularly as a monomer for the cationic ring-opening polymerization to poly(2-alkyloxazoline)s. This type of polymers are under investigation as readily water-soluble and biocompatible materials for biomedical applications.

<span class="mw-page-title-main">Alkyl ketene dimer</span> Class of chemical compounds

Alkyl ketene dimers (AKDs) are a family of organic compounds based on the 4-membered ring system of oxetan-2-one, which is also the central structural element of propiolactone and diketene. Attached to the oxetane ring of technically relevant alkyl ketene dimers there is a C12 – C16 alkyl group in the 3-position and a C13 – C17 alkylidene group in the 4-position.

<span class="mw-page-title-main">2-Methyleneglutaronitrile</span> Chemical compound

2-Methylene glutaronitrile is a dimerization product of acrylonitrile and a starting material for di- and triamines, for the biocide 2-bromo-2-(bromomethyl)pentanedinitrile and for heterocycles, such as 3-cyanopyridine.

Dimethylaminoethyl acrylate or DMAEA is an unsaturated carboxylic acid ester having a tertiary amino group. It is a colorless to yellowish, water-miscible liquid with a pungent, amine-like odor. DMAEA is an important acrylic monomer that gives basic properties to copolymers.

References

  1. ↑ Eller, Karsten; Henkes, Erhard; Rossbacher, Roland; Höke, Hartmut (15 June 2000). "Amines, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a02_001. ISBN   3527306730.
  2. ↑ US 5856555,M. Huser, R. Perron,"Process for the hydrocyanation of organic compounds containing ethylenic unsaturation",published 1999-01-05, assigned to Rhone-Poulenc Fiber & Resin Intermediates
  3. 1 2 US 6242633,J. Fischer, W. Siegel,"Catalyst comprising at least one phosphonite ligand based Nickel (0) complex and method for the production of nitriles",published 2001-06-05, assigned to BASF AG
  4. ↑ US 7816551,T. Jungkamp, R. Baumann, M. Bartsch, G. Haderlein, H. Luyken, J. Scheidel,"Method for producing dinitriles",published 2010-10-19, assigned to BASF AG
  5. 1 2 US 8053594,P. Leconte, P. Marion, R. Jacquot,"Preparation of diesters from imide/dinitrile compounds",published 2011-11-08, assigned to Rhodia Operations
  6. 1 2 3 Vidal, T. (14 June 2012). "Sustainable Solvents Products and Process Innovations" (PDF). Archived from the original (PDF) on 2016-05-12. Retrieved 2016-04-28.
  7. ↑ CH 654576,E.J. Newson, T.-B. Truong,"Verfahren zur Herstellung von 3-Methylpyridin",published 1986-02-28, assigned to Lonza AG
  8. ↑ US 4876348,R. DiCosimo, J.D. Burrington, D.D. Suresh,"Process for making 3-cyanopyridine",published 1989-10-24, assigned to The Standard Oil Co.
  9. ↑ Abe, Nobuyuki; Ichimura, Hisao; Kataoka, Toshiaki; Morishita, Sinji; Shimizu, Shinkichi; Shoji, Takayuki; Watanabe, Nanao (2007). "Pyridine and Pyridine Derivatives". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a22_399.
  10. ↑ US 4987263,G. Cordier,"Preparation of 2-methylpentadiamine",published 1991-01-22, assigned to Rhone-Poulenc Chimie
  11. ↑ US 5719045,J. Heveling, E. Armbruster, L. Utiker, M. Rohner, H.-R. Dettwiler, R.J. Chuck,"Process for preparing nicotinamide",published 1998-02-17, assigned to Lonza AG
  12. ↑ WO 2008074645,P. Pfab, E. Ströfer, C. Knösche, E. Schwab, M. Klötzer, G. Georgi,"Process for preparing 2-methylpentane-1,5-diisocyanate from methylglutaronitrile",published 2008-06-26, assigned to BASF SE
  13. ↑ US 6551804,R. DiCosimo, R.D. Fallon, J.E. Gavagan,"Process for preparing 4-cyanopentanoic acid",published 2003-04-22, assigned to E.I. Du Pont de Nemours and Co.
  14. ↑ US 5814508,R. DiCosimo, R.D. Fallon, J.E. Gavagan, F.E. Herkes,"Preparation of lactams from aliphatic α, ω-dinitriles",published 1998-09-29, assigned to E.I. Du Pont de Nemours and Co.
  15. ↑ F.B. Cooling; et al. (2001). "Chemoenzymatic production of 1,5-dimethyl-2-piperidone". Journal of Molecular Catalysis B: Enzymatic . 11 (4–6): 295–306. doi:10.1016/S1381-1177(00)00150-8.
  16. ↑ US 6261381,G. Wojcik,"Composition and process for cleaning inks from various substrates including printing plates",published 2001-07-17, assigned to MacDermid, Inc.
  17. ↑ INVISTA, Technical Information, DYTEK Methylglutaronitrile (MGN)
  18. ↑ US 20150175515,R. Jacquot, B. Rhers,"Process for preparing diacid compounds",published 2015-06-25, assigned to Rhodia Operations
  19. ↑ Solvay: GPS Safety Summary, Dimethyl 2-methylglutarate Archived 2014-08-05 at the Wayback Machine
  20. ↑ US 20120071686,R. Jacquot, P. Leconte,"Production of diesters from dinitrile compounds",published 2012-03-22
  21. ↑ INVISTA's DBE esters, FlexiSolv DBE esters Archived 2016-11-16 at the Wayback Machine
  22. ↑ US 20130237722,T. Vidal, R. Rached, M. Guglieri,"Process for preparing esteramide compounds",published 2013-09-12, assigned to Rhodia Operations
  23. ↑ US 20140221211,O. Jentzer, M. Guglieri,"Use of esteramides as solvents, novel esteramides and process for preparing esteramides",published 2014-08-07, assigned to Rhodia Operations
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