4107-62-4Relevant academic research and scientific papers
Method for preparing nitrile by reacting acetone cyanohydrin with haloalkane
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Paragraph 0043-0049; 0051-0057; 0067, (2019/08/20)
The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with haloalkane. According to the invention, by using acetone cyanohydrin as a cyaniding reagent, the problems, such as long reaction time, low yield, strict reaction conditions and the like enchanted in an existing preparation method in which highly toxic sodium cyanide or potassium cyanide or expensive trimethylsilyl cyanide is used as a cyanogen source, are solved. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent of a high boiling point dipolar aprotic solvent anda low boiling point aprotic solvent, adding a catalyst lithium hydroxide, stirring at 25-50 DEG C for one hour and then adding a haloalkane for continuous reaction for 2-3 hours; next, adding saturated saline water for washing twice, separating out an organic layer, and boiling off the solvent after drying, thereby obtaining a nitrile compound. The method for preparing a nitrile compound disclosed in the invention is characterized by low reaction toxicity, simple process, easy of operation, low production cost, and a yield of more than 95%.
Generation of the Methoxycarbonyl Radical by Visible-Light Photoredox Catalysis and Its Conjugate Addition with Electron-Deficient Olefins
Slutskyy, Yuriy,Overman, Larry E.
supporting information, p. 2564 - 2567 (2016/07/06)
Visible-light photoredox-catalyzed fragmentation of methyl N-phthalimidoyl oxalate allows the direct construction of a 1,4-dicarbonyl structural motif by a conjugate addition of the methoxycarbonyl radical to reactive Michael acceptors. The regioselectivity of the addition of this alkoxyacyl radical species to electron-deficient olefins is heavily influenced by the electronic nature of the acceptor, behavior similar to that exhibited by nucleophilic alkyl radicals.
Evolution of structure and reactivity in a series of iconic carbenes
Zhang, Min,Moss, Robert A.,Thompson, Jack,Krogh-Jespersen, Karsten
body text, p. 843 - 850 (2012/03/26)
We present experimental activation parameters for the reactions of six carbenes (CCl2, CClF, CF2, ClCOMe, FCOMe, and (MeO) 2C) with six alkenes (tetramethylethylene, cyclohexene, 1-hexene, methyl acrylate, acrylonitrile, and α-chloroacrylonitrile). Activation energies range from -1 kcal/mol for the addition of CCl2 to tetramethylethylene to 11 kcal/mol for the addition of FCOMe to acrylonitrile. A generally satisfactory analysis of major trends in the evolution of carbenic structure and reactivity is afforded by qualitative applications of frontier molecular orbital theory, although the observed entropies of activation appear to fall in a counterintuitive pattern. An analysis of computed cyclopropanation transition state parameters reveals significant nucleophilic selectivity of (MeO)2C toward α-chloroacrylonitrile.
Electrochemical synthesis of adiponitrile from the renewable raw material glutamic acid
Dai, Jian-Jun,Huang, Yao-Bing,Fang, Chi,Guo, Qing-Xiang,Fu, Yao
experimental part, p. 617 - 620 (2012/06/29)
Current affairs: Adiponitrile, used to produce nylon 6.6, is prepared from the renewable compound glutamic acid by an electrochemical route, involving electro-oxidative decarboxylation and Kolbe coupling reactions. The new route is an example of the use of glutamic acid as a versatile substrate in the transformation of biomass into chemicals. Also, it highlights the use of electrochemical methods in biomass conversion.
Synthesis of biobased succinonitrile from glutamic acid and glutamine
Lammens, Tijs M.,N?tre, Jér?me Le,Franssen, Maurice C. R.,Scott, Elinor L.,Sanders, Johan P. M.
experimental part, p. 785 - 791 (2012/05/04)
Succinonitrile is the precursor of 1,4-diaminobutane, which is used for the industrial production of polyamides. This paper describes the synthesis of biobased succinonitrile from glutamic acid and glutamine, amino acids that are abundantly present in many plant proteins. Synthesis of the intermediate 3-cyanopropanoic amide was achieved from glutamic acid 5-methyl ester in an 86 mol % yield and from glutamine in a 56 mol % yield. 3-Cyanopropanoic acid can be converted into succinonitrile, with a selectivity close to 100 % and a 62 % conversion, by making use of a palladium(II)-catalyzed equilibrium reaction with acetonitrile. Thus, a new route to produce biobased 1,4-diaminobutane has been discovered. Copyright
Studies on the titanium-catalyzed cyclopropanation of nitriles
Laroche, Christophe,Harakat, Dominique,Bertus, Philippe,Szymoniak, Jan
, p. 3482 - 3487 (2007/10/03)
The Ti-mediated reaction of Grignard reagents with nitriles was investigated with sub-stoichiometric amounts of titanium isopropoxide. Cyanoesters were converted to spirocyclopropanelactams in good yields using as low as 0.05 eq of Ti(OiPr)sub
Conversion of α-amino acids into nitriles by oxidative decarboxylation with trichloroisocyanuric acid
Hiegel, Gene A.,Lewis, Justin C.,Bae, Jason W.
, p. 3449 - 3453 (2007/10/03)
Trichloroisocyanuric acid oxidation of α-amino acids in water or methanol in the presence of pyridine produces nitriles with one less carbon in good yields and of high purity.
Phase-transfer catalysed (PTC) reactions of 1,1-dichloro-2-cyanocyclopropane with nucleophiles. Identification of intermediates
Jonczyk, Andrzej,Kocmierowski, Tomasz,Zdrojewski, Tadeusz
, p. 295 - 299 (2007/10/03)
An addition-elimination mechanism for PTC reactions of phenols with 1,1-dichloro-2-cyanocyclopropane (1) is supported by trapping of intermediate cyclopropenes 3 and 5. PTC reactions of 1 with a series of phenols 2a-d, thiophenol (2e), alcohols 2f,g and dithioles 11a,b led to formation of disubstituted cyanocyclopropanes 6a-d, 6e, 6f,g or spiroproducts 12a,b, respectively. Under acidic conditions or thermally, dialkoxycyclopropanes 6f,g or spirane 12a were transformed into alkyl 3-cyanopropionates 10f,g and ketene dithioacetal 13a.
Counterattack Reagent: Hexamethyldisilathiane in the Conversion of Nitro Compounds into Nitriles
Tsay, Shwu-Chen,Gani, Paul,Hwu, Jih Ru
, p. 1493 - 1495 (2007/10/02)
Various primary nitro compounds have been treated with KH in tetrahydrofuran and then with Me3SiSSiMe3 to give potassium thiohydroxamates.These salts were neutralized by an acid and then desulphurized by light to afford nitriles in 78-87percent yields.In these reactions, Me3SiSSiMe3 acted as a 'counterattack reagent'.
Cobalt Carbonyl Mediated Michael Addition: Direct Synthesis of Esters Containing Other Functional Groups from Activated Olefins
Sisak, Attila,Ungvary, Ferenc,Marko, Laszlo
, p. 2508 - 2513 (2007/10/02)
Hydrocarbalkoxylation of acrylonitrile with stoichiometric amounts of alcohols in the presence of catalytic amounts of Co2(CO)8 and pyridine bases leads to 2,4-dicyano-2-methylbutanoic acid esters.The yield of these Michael adducts shows a maximum as a function of the pyridine/cobalt ratio.Analogues reactions using equimolar amounts of alcohol, acrylonitrile, and an other activated olefin result in products with at least three different functional groups.Acrylonitrile with pyH gives (1-cyanoethyl)cobalt tetracarbonyl, which is proposed to be the key intermediate of the hydrocarbalkoxylation.This complex may be deprotonated to a "Michael donor" anion, i.e. the Michael adducts are most probably formed in a cobalt-mediated way.The above catalytic system promoted also the Michael addition of some C-H acids to activated olefins under atmospheric conditions.
