2-Methylglutaronitrile

2-Methylglutaronitril Struktur.svg 200px 2-Methylpentanedinitrile 1,3-Dicyanobutane, α-Methylvalerodinitrile 4553-62-2 correct CAS correct FDA EJX3MSL725 20686 19482 CC(CCC#N)C#N 224-923-5 FPPLREPCQJZDAQ-UHFFFAOYSA-N 1S/C6H8N2/c1-6(5-8)3-2-4-7/h6H,2-3H2,1H3 C480967 6 8 2 colorless liquid 0.9548 g/cm3 -45 263 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.Eller Karsten Henkes Erhard Rossbacher Roland Höke Hartmut 15 June 2000 Amines, Aliphatic Ullmann's Encyclopedia of Industrial Chemistry 10.1002/14356007.a02_001 3527306730 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] US 5856555 Process for the hydrocyanation of organic compounds containing ethylenic unsaturation 1999-01-05 1997-04-11 M. Huser, R. Perron Rhone-Poulenc Fiber & Resin Intermediates or phosphite or phosphonite [P(OR)2R] US 6242633 Catalyst comprising at least one phosphonite ligand based Nickel (0) complex and method for the production of nitriles 2001-06-05 1998-09-09 J. Fischer, W. Siegel BASF AG). The mixture contains mainly trans-3-pentenenitrile in addition to the isomers 2-methyl-2-butenenitrile, 4-pentenenitrile and 2-pentenenitrile. 400px|center|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). 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. 400px|center|Umsetzung von Pentennitrilen zu Dinitrilen 2-Methylglutaronitrile can be separated by fractional distillation. US 7816551 Method for producing dinitriles 2010-10-19 2005-01-27 T. Jungkamp, R. Baumann, M. Bartsch, G. Haderlein, H. Luyken, J. Scheidel BASF AG 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.Vidal T. 14 June 2012 Sustainable Solvents Products and Process Innovations http://www.chemspeceurope.com/content-images/main/Conferences/Sustainable-Solvents-Products-and-Process-Innovations_Thierry-Vidal_-RSC-Symposium-2012.pdf 2016-04-28 https://web.archive.org/web/20160512130946/http://www.chemspeceurope.com/content-images/main/Conferences/Sustainable-Solvents-Products-and-Process-Innovations_Thierry-Vidal_-RSC-Symposium-2012.pdf 2016-05-12 dead Applications 2-methylglutaronitrile can be converted to 3-methylpyridine (β-picoline) by partial hydrogenation.CH 654576 Verfahren zur Herstellung von 3-Methylpyridin 1986-02-28 1982-07-29 E.J. Newson, T.-B. Truong Lonza AGUS 4876348 Process for making 3-cyanopyridine 1989-10-24 1985-10-29 R. DiCosimo, J.D. Burrington, D.D. Suresh The Standard Oil Co. 400px|center|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%.Abe Nobuyuki Ichimura Hisao Kataoka Toshiaki Morishita Sinji Shimizu Shinkichi Shoji Takayuki Watanabe Nanao 2007 10.1002/14356007.a22_399 Pyridine and Pyridine Derivatives 978-3527306732 500px|center|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.US 4987263 Preparation of 2-methylpentadiamine 1991-01-22 1988-08-12 G. Cordier Rhone-Poulenc Chimie 400px|center|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.US 5719045 Process for preparing nicotinamide 1998-02-17 1996-10-31 J. Heveling, E. Armbruster, L. Utiker, M. Rohner, H.-R. Dettwiler, R.J. Chuck Lonza AG The racemic diamine can also be used for the preparation of specific polyamides and after reaction with phosgene to form 2-methylpentane diisocyanateWO 2008074645 Process for preparing 2-methylpentane-1,5-diisocyanate from methylglutaronitrile 2008-06-26 2007-12-06 P. Pfab, E. Ströfer, C. Knösche, E. Schwab, M. Klötzer, G. Georgi BASF SE 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.US 6551804 Process for preparing 4-cyanopentanoic acid 2003-04-22 2001-01-22 R. DiCosimo, R.D. Fallon, J.E. Gavagan E.I. Du Pont de Nemours and Co. 400px|center|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,US 5814508 Preparation of lactams from aliphatic α, ω-dinitriles 1998-09-29 1997-08-13 R. DiCosimo, R.D. Fallon, J.E. Gavagan, F.E. Herkes E.I. Du Pont de Nemours and Co.F.B. Cooling et al. Journal of Molecular Catalysis B: Enzymatic 11 4–6 295–306 2001 10.1016/S1381-1177(00)00150-8 Chemoenzymatic production of 1,5-dimethyl-2-piperidone an environmentally compatible solvent.US 6261381 Composition and process for cleaning inks from various substrates including printing plates 2001-07-17 2000-11-09 G. Wojcik MacDermid, Inc. 400px|center|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.INVISTA, Technical Information, DYTEK Methylglutaronitrile (MGN) 600px|center|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%.US 20150175515 Process for preparing diacid compounds 2015-06-25 2013-06-26 R. Jacquot, B. Rhers Rhodia Operations 400px|center|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-methylglutarateSolvay: GPS Safety Summary, Dimethyl 2-methylglutarate https://web.archive.org/web/20140805131749/http://www.solvay.com/en/binaries/Dimethyl%202-methylglutarate_GPS_rev0_Oct13%28Solvay%29-164698.pdf 2014-08-05 in the presence of titanium dioxideUS 8053594 Preparation of diesters from imide/dinitrile compounds 2011-11-08 2007-07-05 P. Leconte, P. Marion, R. Jacquot Rhodia Operations or lanthanum oxide.US 20120071686 Production of diesters from dinitrile compounds 2012-03-22 2008-10-21 R. Jacquot, P. Leconte 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 as a substitute for acetone, dichloromethane, N-methylpyrrolidone and the like. 500px|center|Diester aus 2-MGN-Imid The ester mixture is very similar to so-called dibasic esters, which are commercially available as FlexiSolv DBE esters.INVISTA's DBE esters, FlexiSolv DBE esters https://web.archive.org/web/20161116153146/http://flexisolv.com/en/products/dbe-esters.html 2016-11-16 The diester can be selectively converted into a mixture of 1- or 5-substituted methyl ester amides with dimethylamine in methanol/sodium methoxide,US 20130237722 Process for preparing esteramide compounds 2013-09-12 2011-06-09 T. Vidal, R. Rached, M. Guglieri Rhodia Operations which is used under the name Rhodiasolv Polarclean as formulation auxiliaries for crop protection preparations. 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).US 20140221211 Use of esteramides as solvents, novel esteramides and process for preparing esteramides 2014-08-07 2014-04-09 O. Jentzer, M. Guglieri Rhodia Operations References Category:Alkanedinitriles