61892-68-0Relevant articles and documents
Synthesis of α-aminonitriles using aliphatic nitriles, α-amino acids, and hexacyanoferrate as universally applicable non-toxic cyanide sources
Nauth, Alexander M.,Konrad, Tim,Papadopulu, Zaneta,Vierengel, Nina,Lipp, Benjamin,Opatz, Till
supporting information, p. 4217 - 4223 (2018/09/29)
In cyanation reactions, the cyanide source is often directly added to the reaction mixture, which restricts the choice of conditions. The spatial separation of cyanide release and consumption offers higher flexibility instead. Such a setting was used for the cyanation of iminium ions with a variety of different easy-to-handle HCN sources such as hexacyanoferrate, acetonitrile or α-amino acids. The latter substrates were first converted to their corresponding nitriles through oxidative decarboxylation. While glycine directly furnishes HCN in the oxidation step, the aliphatic nitriles derived from α-substituted amino acids can be further converted into the corresponding cyanohydrins in an oxidative C-H functionalization. Mn(OAc)2 was found to catalyze the efficient release of HCN from these cyanohydrins or from acetone cyanohydrin under acidic conditions and, in combination with the two previous transformations, permits the use of protein biomass as a non-toxic source of HCN.
Bio-based nitriles from the heterogeneously catalyzed oxidative decarboxylation of amino acids
Claes, Laurens,Matthessen, Roman,Rombouts, Ine,Stassen, Ivo,De Baerdemaeker, Trees,Depla, Diederik,Delcour, Jan A.,Lagrain, Bert,De Vos, Dirk E.
, p. 345 - 352 (2015/01/30)
The oxidative decarboxylation of amino acids to nitriles was achieved in aqueous solution by in situ halide oxidation using catalytic amounts of tungstate exchanged on a [Ni,Al] layered double hydroxide (LDH), NH4Br, and H2O2 as the terminal oxidant. Both halide oxidation and oxidative decarboxylation were facilitated by proximity effects between the reactants and the LDH catalyst. A wide range of amino acids was converted with high yields, often > 90%. The nitrile selectivity was excellent, and the system is compatible with amide, alcohol, and in particular carboxylic acid, amine, and guanidine functional groups after appropriate neutralization. This heterogeneous catalytic system was applied successfully to convert a pro-tein-rich byproduct from the starch industry into useful biobased N-containing chemicals.
Decarboxylation of a Wide Range of Amino Acids with Electrogenerated Hypobromite
Matthessen, Roman,Claes, Laurens,Fransaer, Jan,Binnemans, Koen,De Vos, Dirk E.
, p. 6649 - 6652 (2016/02/19)
Bromide-assisted electrochemical decarboxylation efficiently produces valuable nitriles in high yields from a wide range of naturally occurring amino acids in a single step. Bromide salts are used as both redox mediators and supporting electrolytes in a simple one-compartment setup. As demonstrated for lysine, the selectivity of the decarboxylation can be tuned towards nitriles, amines or amides. An electrochemical system is developed that allows the selective decarboxylation of a wide range of amino acids. Valuable nitriles are obtained in high yields in a single step by using bromide salts as both redox mediators and supporting electrolytes. The product selectivity of lysine can be tuned towards nitriles, amines, or amides.
Hydrolysis of nitrile in presence of different zeolite catalysts under microwave IR-radiation
Singh, Ravinder,Kumar, Ramesh
experimental part, p. 1403 - 1404 (2012/09/22)
The hydrolysis of nitriles in presence of different zeolite catalysts under microwave irradiations gives corresponding amide in high yield in few minutes.
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
Hydrolysis of nitrile in presence of NaY zeolite under microwave irradiation
Singh, Ravinder,Kumar, Ramesh
experimental part, p. 317 - 320 (2012/02/04)
The hydrolysis of nitriles in presence of NaY zeolite under microwave irradiations gives corresponding amide in high yield in few minutes.
Role of chloride in the oxidative decarboxylation of amino acids by chloramine-T
Gowda, B. Thimme,Quine, S. Darlin,Krishna Kumar
, p. 413 - 420 (2007/10/03)
Kinetics of oxidative decarhoxylation of amino acids by chloramine-T in the presence of chloride have been studied in aqueous perchloric acid over a wide range. The rate-[H+] plots show nearly bell-shaped profiles in the presence of added chloride. The rate-dependence in [CAT] changes from second order to first order as [H+] and [Cl-] are varied. The reactions generally show fractional order kinetics in [AA] and inverse dependence in [H+] except in the acid range 0.05-0.20 mol dm-3. Mechanisms consistent with the observed results are discussed. The rate-limiting steps have been identified and constants of these steps calculated. Activation parameters corresponding to these steps have also been computed. Validity of Taft equation has been tested. The study establishes the significant role of chloride in chloramine-T oxidations in acid medium. The chloride effect is more pronounced at high acid concentrations.
NaY zeolite: A useful catalyst for nitrile hydrolysis
Milli?, Dragana R.,Opsenica, Dejan M.,Adnadevi?, Borivoje,?olaja, Bogdan A.
, p. 118 - 126 (2007/10/03)
The NaY zeolite catalysed hydrolysis of nitriles to primary amides is reported. It is found that aryl nitriles with strong electron-withdrawing substituents and cyanopyridines are readily hydrolysed in the water suspension, while aliphatic nitriles do not react.
Synthesis of novel analogs of acetyl coenzyme A: Mimics of enzyme reaction intermediates
Martin, David P.,Bibart, Richard T.,Drueckhammer, Dale G.
, p. 4660 - 4668 (2007/10/02)
An improved method for the synthesis of analogs of coenzyme A (CoA) and its thioesters, which are modified in the thiol or thioester moiety, has been developed using a combination of chemical and enzymatic reactions. The enzymes catalyzing the last two steps of CoA biosynthesis were used to prepare a CoA analog (Ic) in which an amide bond is replaced by a thioester bond and the thiol group is replaced by a methyl group. Reaction of Ic with a primary amine in aqueous solution results in aminolysis of the thioester linkage to form the desired CoA analog. Reaction with different amines permits the introduction of a variety of functional groups in place of the normal thiol or thioester group. This methodology has been used in the synthesis of five new analogs of acetyl-CoA in which the thioester sulfur is replaced by a methylene group and the acetyl group is replaced by carboxylate (14a), nitro (14b), carboxamide (14c), methyl sulfoxide (14d), and methyl sulfone (14e) groups. 14a-c were designed to mimic the possible enolate or enol intermediate in the reaction of citrate synthase and related enzymes. 14a and 14c are potent inhibitors of citrate synthase, with K(i) values 1000- and 570-fold lower than the K(m) for acetyl-CoA, respectively. CD titrations indicate that 14a and 14c have low affinity for citrate synthase in the absence of oxaloacetate, consistent with their recognition as enol or enolate analogs. 14b is a poor inhibitor of citrate synthase, with affinity slightly lower than that for acetyl-CoA. These results are consistent with generation of the enol form of acetyl-CoA as the nucleophilic intermediate in the reaction of citrate synthase. 14d and 14e were designed to mimic the tetrahedral intermediate or transition state in the reaction of chloramphenicol acetyltransferase and related acetyl-CoA-dependent acetyltransferases. Both compounds are poor inhibitors of chloramphenicol acetyltransferase, with affinities slightly lower than that of acetyl-CoA, indicating that these compounds are not good mimics of the enzyme-bound tetrahedral intermediate or transition state.
Chloraminometric Reactions: Kinetics and Mechanisms of Oxidations of Amino-acids by Sodium N-Chlorotoluene-p-sulphonamide in Acid and Alkaline Media
Gowda, Basavalinganadoddy Thimme,Mahadevappa, Darndinasivara S.
, p. 323 - 334 (2007/10/02)
Available data on the kinetics of oxidations of amino-acids by sodium N-chloro toluene-p-sulphonamide (chloramine T) in acid and alkaline media have been critically examined.General mechanisms have been proposed for both acid and alkaline medium oxidations.The oxidation process in acid media has been shown to proceed via two paths, one involving the direct interaction of N-chlorotoluene-p-sulphonamide (RNHCl) with the neutral amino-acid in a slow step leading to the formation of the monochloroamino-acid which subsequently interacts with another molecule of RNHCl, in a fast step, to give the NN-dichloroamino-acid which in turn undergoes molecular rearrangement and elimination to yield the products, and the other involving the interaction of Cl2 or H2OCl(1+), produced from the disproportionation of RNHCl in the presence or absence of Cl(1-), with the substrate to give the products.In the alkaline medium mechanisms involving the interaction of RNHCl, HOCl, RNCl(1-), and OCl(1-) with the substrate are proposed.The mechanisms proposed and the derived rate lows are consistent with the observed kinetics.The rate constants predicted by the derived rate laws, as the concentrations of substrate and Cl(1-) ion change, are in excellent agreement with the observed rate constants thus further verifying the rate laws and hence the proposed mechanisms.
