Nitriles propionitrile

Catalysts show remarkable product variation in hydrogenation of simple nitriles. Propionitrile, in neutral, nonreactive media, gives on hydrogenation over rhodium-on-carbon high yields of dipropylamine, whereas high yields of tripropylamine arise from palladium or platinum-catalyzed reductions (71). Parallel results were later found for butyronitrile (2S) and valeronitrile (74) but not for long-chain nitriles. Good yields of primary aliphatic amines can be obtained by use of cobalt, nickel, nickel boride, rhodium, or ruthenium in the presence of ammonia (4J 1,67,68,69). 

Nitriles Propionitrile, acrylonitrile Separated on a C-18 reverse phase column and determined by UV detector... 

Nitrile Propionitrile. Ethyl cyanide. Cyanoethane. Liq. with ethereal odour. Part. misc. H2O. Fp —103.5 . Bp 97 . 

The formation of ethyl cyano(pentafluorophenyl)acetate illustrates the intermolecular nucleophilic displacement of fluoride ion from an aromatic ring by a stabilized carbanion. The reaction proceeds readily as a result of the activation imparted by the electron-withdrawing fluorine atoms. The selective hydrolysis of a cyano ester to a nitrile has been described. (Pentafluorophenyl)acetonitrile has also been prepared by cyanide displacement on (pentafluorophenyl)methyl halides. However, this direct displacement is always aecompanied by an undesirable side reaetion to yield 15-20% of 2,3-bis(pentafluoro-phenyl)propionitrile. 

Nitriles are organic derivatives of hydrocyanic acid in which the substituting group is attached to carbon. Their formula is R.C N. Because most nitriles can be derived from corresponding acid amides, R.CO.NH2, by removal of w, they are called nitriles. For instance, the compd CH3.CN is called acetonitrile because it is derived from acetamide. It can also be called methyl cyanide. The compd C2HS.CN is called either propionitrile or ethyl cyanide, etc The first nitrile to be prepared was propionitrile which J. Pelouze obtained in 1834 by distg Ba ethyl sulfate with K cyanide... 

Vesey et al. 1976) and a series of commercially important, simple, aliphatic nitriles (e.g., acetonitrile, propionitrile, acrylonitrile, n-butyronitrile, maleonitrile, succinonitrile) (Willhite and Smith 1981) release cyanide upon metabolism. These drugs and industrial chemicals have been associated with human exposure to cyanide and have caused serious poisoning and, in some cases, death. 

This point is illustrated by a second example. A vapor-phase spectrum of propionitrile was obtained and its digitization is shown in Table III. For the sake of example, assume the scientist entered the 2246 cm peak as average rather than sharp. The interpretation would result in likelihoods of 0.90 for isocyanate and 0.30 for nitrile. Performing the interpretation with the tracing function turned on would quickly show that the rules base the distinction between isocyanate and propionitrile very heavily on the width of the peak in the vicinity of 2260 cm . Reinterpreting this spectrum with the correct, sharp width entered for the 2246 cm peak results in a nitrile likelihood of 0.50 and isocyanate of 0.40. 

In order to obtain maximum catalytic TON, pyridine yields, nitrile conversions, as well as high pyridine/benzene ratios in the product, more than 60 [YCoL] complexes were systematically investigated for the catalytic cotrimerization of propionitrile and acetylene [Eq.(9)J [85AG264, 85AG(E)248]. 

The molecular ion peaks of aliphatic nitriles (except for acetonitrile and propionitrile) are weak or absent, but the M + 1 peak can usually be located by its behavior on increasing inlet pressure or decreasing repeller voltage (Section 2.5). A weak but diagnostically useful M - 1 peak is formed by loss of an a hydrogen to form the stable ion RCH—C=N,+ <—> RCH=C=N+. 

The electrolyte solution used in the DSSC contains I /I3 redox ions, which carry electrons between the Ti02 photoelectrode and the counterelectrode. Mixtures of 0.05-0.1 M of I2 and 0.1-0.5 M of an iodide salt such as Lil, Nal, KI, tetraalkylammonium iodides (R4NI), and imidazolium iodides are dissolved in organic solvents. As an organic solvent, acetonitrile, propionitrile, methoxyaceto-nitrile, propylene carbonate, and their mixtures are used. The performance of the DSSC depends on the counter cations of the applied iodide salt such as Li+, Na+, K +, and R4N+. The cell performance varies because the cations influence the ion conductivity of the electrolyte solution and they adsorb on the 2 surface... 

With DIOP-Pd(0) or -Ni(0) complexes as catalysts, moderate optical yields of up to 35% have been observed (126). Norbomene is convertible to the exo nitrile with up to 40% ee when a BINAP-Pd(0) complex is used (Scheme 57) (127). Ni(0) complexes of sugar-derived 1,2-diol phosphinites catalyze highly selective asymmetric addition of hydrogen cyanide to vinylarenes (128). This method gives the 2-naphthalene-2-propionitrile precursors of nonsteroid anti-inflammatory agents in up to 85% ee and in high yield. 

The title olefins form complexes with Ni(0) with equilibrium constants for formation decreasing in the order ethylene > styrene > propylene 1-hexene > disubstituted alkenes (28). With ethylene and styrene the (olefin)NiL2 complexes have been isolated with L = P(0-o-tolyl)3. Addition of HCN to solutions of the pure olefin complexes results in rapid and complete conversion to alkylnickel cyanide intermediates which are spectroscopically detectable subsequent C—C coupling gives the observed nitrile products propionitrile from ethylene and (predominantly) 2-phenylpropion-itrile from styrene (47). The same alkyl intermediates are formed when ethylene and styrene are added to HNiL3CN [L = p(0-o-tolyl)3]. 

Nitriles may be prepared by several methods (1). The first nitrile to be prepared was propionitrile, which was obtained in 1834 by distilling barium ethyl sulfate with potassium cyanide. This is a general preparation of nitriles from sulfonate salts and is referred to as the Pelouze reaction (2). Although not commonly practiced today, dehydration of amides has been widely used to produce nitriles and was the first commercial synthesis of a nitrile. The reaction of alkyl halides with sodium cyanide to produce nitriles (eq. 1) also is a general reaction with wide applicability ... 

The propensity of nitriles to release cyanide subsequent to metabolism is the basis of their acute toxicity. Nitriles that form tertiary radicals at their alpha carbon atoms (eg, isobutyronitrile, 2-methylbutyronitrile) are substantially more acutely lethal than nitriles that form secondary radicals at their alpha carbons (eg, butyronitrile, propionitrile). Cyanohydrins are acutely toxic because they are unstable and release cyanide quickly. Alpha-aminonitriles are also acutely toxic, presumably by analogy with cyanohydrins. 

Nitrile-stabilized anions, generated for example by lithiation of benzyl cyanide and propionitrile, have been added diastereoselectively to aromatic aldimines.50 Acid workup gives /5-cyano amines. Alternatively, addition of RX gives /3-R-substituted-/3-cyanoamines. The factors determining des in both reaction versions have been investigated. 

Nitriles Unlikely to be detected except in case of acetonitrile (CH,CN) and propionitrile (C2H5CN) M + 1 ion may appear (especially at higher pressures) M - 1 peak is weak but detectable (R-CH=C=N ) base peak at m/e = 41 (CH2=C=NH) McLafferty rearrangement possible loss of HCN is case of cyanobenzenes... 

Nitriles are cyanogenic substances — substances that produce cyanide when metabolized. It is likely that nitriles are teratogens because of maternal production of cyanide in pregnant females. A study of the teratogenic effects on rats of saturated nitriles, including acetonitrile, propionitrile, and n-butyronitrile, and of unsaturated nitriles, including acrylonitrile, methacrylonitrile, allylnitrile, m-2-pcntenenitrile, and 2-chloroacrylonitrile, has shown a pattern of abnormal embryos similar to those observed from administration of inorganic cyanide.6... 

Ketones Ketones with fewer than six carbon atoms Nitriles Acetonitrile Propionitrile Sulfonic acids Sodium or potassium salts of most are acceptable B. Inorganic chemicals Cations Anions... 

A large excess of ammonia suppresses formation of di- and trialkylamines. With a rhodium-on-carbon catalyst in process conditions of 75°C and 50 psig plus continuous removal of ammonia, the reduction of propionitrile with hydrogen proceeds with greater than 85% selectivity for di-n-propylamine, with 2 to 5% mono-n-propylamine coproduct. Several companies produce amines in the C 2 to Ci8 range from fatty nitriles by this route116. 

Cobalt boride catalysts have been shown to be highly active and selective in the hydrogenation of nitriles to primary amines.103,104 Barnett used Co boride (5%) supported on carbon for the hydrogenation of aliphatic nitriles and obtained highest yields of primary amines among the transition metals and metal borides investigated including Raney Co.104 An example with propionitrile, where a 99% yield of propylamine was obtained in the presence of ammonia, is seen in eq. 7.29. 

High yields of primary amines have also been obtained over cobalt boride as catalyst,26,53,54 which has been found to be not only highly selective but also less inhibited by solvent and ammonia than other cobalt and nickel catalysts in hydrogenation of nitriles.26 The hydrogenation of propionitrile in isopropyl alcohol over cobalt boride (5% on C) in the presence of 15 1 molar ratio of ammonia to the nitrile gave propylamine in a high yield of 99% (eq. 7.29). 

Lithium chloride is soluble in many organic solvents 1 among them are alcohols, such as methyl alcohol, ethyl alcohol, higher alcohols, and glycerol aldehydes and ketones, such as acetaldehyde, paraldehyde, and acetone fatty acids, such as formic acid and acetic acid nitriles, such as acetonitrile and propionitrile phenol and bases, such as pyridine. Solution is sometimes accompanied by evolution of heat and formation of compounds, examples of those isolated 2 being... 

Nitriles can condense cyclically with aldehydes, in the presence of acid, to yield hexahydro-.s-triazines e.g., propionitrile and formaldehyde give the hexahydro-l,3,5-tripropionyl-s-triazine (25b).62 When benzo-nitrile (1 mole) and benzoyl chloride (2 moles) were heated to 150° with zinc (or stannic) chloride, a high yield of 2,4,6-triphenyl-3,5-diaza-pyrylium salt (46) was formed,623 which was converted into 2,4,6-triphenyl-s-triazine by ammonia. 

Among aliphatic nitriles, unbranched saturatured or unsaturated compounds with a medium chain length (for instance, propionitrile, butyronitrile, hexaneni-trile, and acrylonitrile) are hydrolyzed with the highest relative rate (about 20-35% of that for benzonitrile) by aromatic nitrilases. Branched nitriles are in general poor substrates of these enzymes but, for instance, isobutyronitrile is one of the best substrates of the aliphatic nitrilase from R. rhodochrous K22 [28]. 

The propionitrile nitrile hydratase-catalyzed reaction presented kinetics inhibited by high substrate concentrations that were clearly evidenced in the CSMR, as revealed in [33]. The kinetic parameters for nitrile hydratase-catalyzed reactions of... 

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