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A growing and useful class of alkene coupling reactions involve hydrogen atom transfer (HAT) from a metal-hydride species to an alkene to form a free radical, which is responsible for subsequent bond formation. Here, we use a combination of experimental and computational investigations to map out the mechanistic details of iron-catalyzed reductive alkene cross-coupling, an important representative of the HAT alkene reactions. We are able to explain several observations that were previously mysterious. First, the rate-limiting step in the catalytic cycle is the formation of the reactive Fe-H intermediate, elucidating the importance of the choice of reductant. Second, the success of the catalytic system is attributable to the exceptionally weak (17 kcal/mol) Fe-H bond, which performs irreversible HAT to alkenes in contrast to previous studies on isolable hydride complexes where this addition was reversible. Third, the organic radical intermediates can reversibly form organometallic species, which helps to protect the free radicals from side reactions. Fourth, the previously accepted quenching of the postcoupling radical through stepwise electron transfer/proton transfer is not as favorable as alternative mechanisms. We find that there are two feasible pathways. One uses concerted proton-coupled electron transfer (PCET) from an iron(II) ethanol complex, which is facilitated because the O-H bond dissociation free energy is lowered by 30 kcal/mol upon metal binding. In an alternative pathway, an O-bound enolate-iron(III) complex undergoes proton shuttling from an iron-bound alcohol. These kinetic, spectroscopic, and computational studies identify key organometallic species and PCET steps that control selectivity and reactivity in metal-catalyzed HAT alkene coupling, and create a firm basis for elucidation of mechanisms in the growing class of HAT alkene cross-coupling reactions.

The mechanistic study of Ir(III) chloride catalyzed oxidation of Val has been studied by by N-bromophthalimide (NBP) in aqueous perchloric acid medium at 303 K. The reaction followed first order kinetics with respect to [NBP] and zero order kinetics with respect to [Val]. At lower concentration range of Ir(III) chloride, the reaction followed first order kinetics while tending to zero order at its higher concentration. A negative effect was observed for [H+] and [NHP] (phthalimide) whereas variation in [Hg(OAc)2] (mercuric acetate), [Cl-], ionic strength (I) and dielectric constant of the medium did not bring about any significant change on the rate of reaction. The rate constants observed at five different temperatures (298 K-318 K) were used to calculate the activation parameters. A plausible mechanism from the results of kinetic studies, reaction stoichiometry and product analysis has been proposed. Copyright Taylor & Francis Group, LLC.

We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.

We report herein an efficient, economical, and scalable trifluoromethylthiolation of aldehydes to generate trifluoromethylthioesters via a visible light-promoted radical process. The transformation features cheap reagents, simple operation, a broad substrate scope, and especially no metal involved in the reaction. Trifluoromethylthiolations of several complex aldehyde-containing bioactive compounds have been realized; thus the approach has the potential to be an important tool for the late-stage functionalization of advanced synthetic intermediates and bioactive molecules, and should have many applications in medicinal chemistry. This journal is

Difluoromethylselenoester compounds, another important kind of organoselenium compounds, are reported herein for the first time. They can be efficiently synthesized from aldehydes and BnSeCF2H. The synthetic method features mild reaction conditions, broad substrate scope, good tolerance of functional groups, and importantly, no metal is involved in the reaction.

The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.

The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)

Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.

The effect of viscosity on the diffusion efficiency (Fdif) of an organic radical pair in a solvent cage and the termination mechanism, that is, the selectivity of disproportionation (Disp) and combination (Comb) of the geminated caged radical pair and the diffused radicals encountered, were investigated quantitatively by following the photolysis of dimethyl 2,2′-azobis(2-methylpropionate) (V-601) in the absence and presence of PhSD. Fdif and Disp/Comb selectivity outside the cage [Disp(dif)/Comb(dif)] are highly sensitive to the viscosity. In contrast, the Disp/Comb selectivity inside the cage [Disp(cage)/Comb(cage)] is rather insensitive. The difference in viscosity dependence between Disp(cage)/Comb(cage) and Disp(dif)/Comb(dif) is explained by the spin state of the radical pair inside and outside the cage and the spin state dependent configurational changes of the radical pair upon their collision. Given that the configurational change of the radicals associates the displacement and reorganization of solvents around the radicals, the termination outside the cage, which requires larger change than that inside the cage, is highly viscosity dependent. Furthermore, while the bulk viscosity of each solvent shows good correlation with Fdif and Disp/Comb selectivity, microviscosity is the better parameter predicting Fdif and Disp(dif)/Comb(dif) selectivity regardless of the solvents.

Homoleptic uranium(IV) amidate complexes have been synthesized and applied as single-source molecular precursors for the chemical vapor deposition of UO2 thin films. These precursors decompose by alkene elimination to give highly crystalline ph

Cyanoisopropyl radicals, generated thermally by the decomposition of azobis(isobutyronitrile) (AIBN), participate in reductive radical termination (RRT) under the combined effect of copper(I) complexes and proton donors (water, methanol, triethylammonium salts) in acetonitrile or benzene. The investigated copper complexes were formed in situ from [CuI(MeCN)4]+BF4- in CD3CN or CuIBr in C6D6 using tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA), and 2,2′-bipyridine (BIPY) ligands. Upon keeping all other conditions constants, the impact of RRT is much greater for the Me6TREN and TPMA systems than for the BIPY system. RRT scales with the proton donor acidity (Et3NH+ a‰? H2O > CH3OH), it is reduced by deuteration (H2O > D2O and CH3OH > CD3OD), and it is more efficient in C6D6 than in CD3CN. The collective evidence gathered in this study excludes the intervention of an outer-sphere proton-coupled electron transfer (OS-PCET), while an inner-sphere PCET (IS-PCET) cannot be excluded for coordinating proton donors (water and methanol). On the other hand, the strong impact of RRT for the noncoordinating Et3NH+ in CD3CN results from the formation of an intermediate CuI-radical adduct, suggested by DFT calculations to involve binding via the N atom to yield keteniminato [L/Cu-N=C=CMe2]+ derivatives with only partial spin delocalization onto the Cu atom.

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.

The invention discloses a aryloximes and continuous synthesis of nitrile compounds. The method comprises the following steps: continuously in the reactor in the continuous instantaneous generation free hydroxylamine, free hydroxylamine with the RCH2 CHO condensation reaction, to obtain the oxime; wherein R is straight or branched alkyl, substituted or non-substituted aryl group, a substituted or non-substituted heterocyclic or cyclic alkyl, [...] a step through the continuous programme dewatered to form a nitrile. The application of the technical scheme of the invention, continuous instant generating free hydroxylamine, avoids a great deal of free hydroxylamine to the process production risks, through the continuous reaction device to carry out the reaction, simplified neutralization in the prior art, extraction, concentration and the like, the production cost is reduced. And in the course of the reaction, the solvent can accomplish the complete recovery, three waste emissions can be greatly reduced, and post-processing operation and the reaction operation is simplified, the production cost is reduced and the cost of raw material, also improves the amplifying a producing process of the security. (by machine translation)

The invention relates to a method for preparing 2-amino-2-methyl-1-propanol. The method comprises the following steps: 1) enabling 2-chloropropane and sodium cyanide to react to generate 2-methyl propionitrile; 2) performing aldol condensation reaction on the 2-methyl propionitrile and formaldehyde so as to generate 2,2-dimethyl-3-hydroxy propionitrile; 3) performing hydrolysis reaction on 2,2-dimethyl-3-hydroxy propionitrile so as to generate 2,2-dimethyl-3-hydroxy propanamide; and 4) performing Hofmann degradation on the 2,2-dimethyl-3-hydroxy propanamide, thereby obtaining 2-amino-2-methyl-1-propanol. The method is cheap and easy in obtaining of raw materials of different steps, simple in reaction process, free of hash reaction condition, remarkable in cost advantage, high in yield, low in pollution and easy in product purification.

The tandem reaction is a growing field to yield important advances toward green and sustainable chemistry. Herein, we report a bifunctional manganese oxide catalyst with an interface binding redox phase (α-MnO2) and a basic phase (NaxMnO2). The molar ratio of NaOH/Mn plays a great role in the formation of α-MnO2/NaxMnO2. The sodium cation is essential for the formation of a basic NaxMnO2 phase while the potassium cation promotes the formation of a redox-active α-MnO2 phase. The interface structure of α-MnO2/NaxMnO2 geometrically favors the ammoxidation-Pinner tandem reaction to synthesize imidates in a 58-96% yield from aldehydes. Thus a phase collaborative effect is observed. In the ammoxidation process, the redox cycle of MnIV/MnIII is involved and the lattice oxygen in the α-MnO2 phase acts as an active oxygen species. The O-H in methanol is activated and dissociated on the basic sites of NaxMnO2 to the adsorbed methoxyl species to facilitate the Pinner synthesis. This approach bypasses the conventional synthesis of imidates, which suffer from harsh reaction conditions and the requirement for multiple steps.

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.

Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent. This journal is

Intermetallic Pd3Pb supported on Al2O3 can act as a highly efficient heterogeneous catalyst for the oxidation of various amines including primary, secondary, aromatic, aliphatic, and cyclic amines. The Royal Society of Chemistry 2014.

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.

An effective method for one-step synthesis of nitriles employing C 2-C8 fatty primary alcohols and ammonia over 5%Cu/m-ZrO2 has been found. The conversion of alcohols and selectivity of nitriles obtained are > 96 and > 87 wt.%, respectively, and are obviously influenced by the C2-substitution rather than the chain length of fatty primary alcohols. Cu/m-ZrO2 was characterized by XRD, H 2-TPR, CO2-TPD and NH3-TPD. It is revealed that a substantial amount of Cu species over m-ZrO2 is in highly dispersed CuO. A plausible mechanism is proposed and supported by different experiments, and aldehyde generation is an important step in the reaction mechanism.

An effective method for one-step synthesis of nitriles employing C2-C8 fatty primary alcohols and ammonia over 5%Cu/m-ZrO2 has been found. The conversion of alcohols and selectivity of nitriles obtained are > 96 and > 87 wt.%, respectively, and are obviously influenced by the C2-substitution rather than the chain length of fatty primary alcohols. Cu/m-ZrO2 was characterized by XRD, H2-TPR, CO2-TPD and NH3-TPD. It is revealed that a substantial amount of Cu species over m-ZrO2 is in highly dispersed CuO. A plausible mechanism is proposed and supported by different experiments, and aldehyde generation is an important step in the reaction mechanism.

The oxidative conversion of alcohols or aldehydes to the corresponding nitriles in moderate to good yields was easily achieved by treatment of H 5IO6 and KI in aqueous NH3. This simple and one-pot system provides easy workup and separation of the product. Copyright

High catalytic activity and selectivity has been demonstrated for the oxidation of both aliphatic and aromatic amines to nitriles under benign conditions with dioxygen or air using the Ru2Cl4(az-tpy) 2 complex. The conversion was found to be strongly influenced by the alkyl chain length of the reactant with shorter chain amines found to have lower conversions than those with longer chains. Importantly, by using the ruthenium terpyridine complex functionalized with azulenyl moiety at the 4 position of central pyridine core provided a much higher reactivity catalyst compared with a series of ruthenium terpyridine-based ligand complexes reported. Mechanistic studies using deuterated benzylamine demonstrated the importance of RuOH in this reaction.

A Zn30Cr4.5/γ-Al2O3 bimetallic catalyst that can perform coupled dehydrogenation and hydrogenation reactions was prepared for the amination of allyl alcohol to propionitrile. During the catalysis, the hydrogen derived from the dehydrogenation of the alcohol and imine acted as an in situ source for the hydrogenation of the carbon-carbon double bond. The catalyst exhibited good performance for the reaction at atmospheric ammonia pressure. The parameters that affect the catalyst performance were studied thoroughly, and an optimized process for synthesizing propionitrile from allyl alcohol and ammonia over the catalyst was obtained. Under the optimized conditions, the propionitrile yield was greater than 65%. The characterization results indicated that the dehydrogenation reaction mainly occurred on the Lewis acid sites and revealed that ZnAl 2O4 is the active species for the coupled dehydrogenation-hydrogenation reactions. Chromium doping of the γ-Al 2O3-supported zinc catalyst Zn30/γ- Al2O3 resulted in a decrease in the size of the ZnAl 2O4 crystallites, which was favorable for the dehydrogenation-hydrogenation reactions. The characterization results also revealed that the catalyst deactivation was due to carbon deposition on the catalyst during the catalytic run. The catalyst could be reactivated by blowing air into the reactor at a high temperature.

A GC-MS analysis of the azobisisobutyronitrile thermal decomposition products of in solutions at 80 C showed that the ratio of recombination and disproportionation rates of the cyanoisopropyl radical does not depend on the medium viscosity, but increases when the internal pressure of the solvent increases according to the log(k dispr/k rec) = -1.25 + 0.096 P int 0.5 law. This means that the activation volume corresponding to recombination is larger than that corresponding to disproportionation. It follows from the relationship log(k dispr/k rec) = (ΔV rec ≠ - Δv dispr ≠)ΔP/RT that, for the decomposition of the substrate in benzene under a pressure of 0.5-4.0 kbar, the difference between the activation volumes is ΔV rec ≠ - ΔV dispr ≠ = 8 cm3/mol.

Megawatt KrF laser gas-phase photolysis of benzene and acetonitrile-benzene mixture was studied by using mass spectroscopy-gas-chromatography and Fourier transform infrared spectroscopy for analyses of volatile products, and by Fourier transform infrared, Raman and X-ray photoelectron spectroscopy, electron microscopy and magnetization measurements for analyses of solid products deposited from the gas-phase. The results are consistent with carbonization of benzene and decomposition of non-absorbing acetonitrile in carbonizing benzene through collisions with excited benzene and/or its fragments. The solid products from benzene and acetonitrile-benzene mixture have large surface area and are characterized as nanomagnetic amorphous carbonaceous soot containing unsaturated C centers prone to oxidation. The nanosoot from acetonitrile-benzene mixture incorporates CN groups, confirms reactions of benzene fragments with CN radical and has a potential for modification by reactions at the CN bonds.

Propylphosphonic anhydride has been demonstrated to be an efficient reagent for the transformation of aromatic, heteroaromatic, and aliphatic aldehydes to respective nitriles in excellent yields. This procedure offers simple and one-pot access to nitriles and highlights the synthetic utility of T3P as a versatile reagent in organic chemistry. Georg Thieme Verlag Stuttgart - New York.

[Chemical Equation Presented] Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs with use of Pd2(dba) 3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement.

Radical-ion salts bis(biphenyl)chromium(i) 1,4-di(2-cyanoisopropyl)-1,4- dihydrofulleride [(Ph2)2Cr]+?[1,4- (CMe2CN)2C60]-? and bis(biphenyl)chromium(i) 1-(2-cyanoisopropyl)-1,2-

(Chemical Equation Presented) Arylthiols serve as excellent environmentally benign reducing agents for organotellurium, organostibine, and organobismuthine compounds under radical conditions. Both small molecules and macromolecules possessing these heteroatom groups are reduced under moderate thermal conditions to give near quantitative yields in most cases. The reduction shows high chemoselectivity with respect to the heteroatom compounds; the reactivity decreases in the order alkylbismuthines, alkylstibines, and alkyltellurides, while simple alkyl iodides could not be reduced. Alkyltellurides are selectively reduced in the presence of alkyl iodides even when an excess amount of arylthiol is used. Furthermore, alkylstibines are also selectively reduced in the presence of alkyltellurides. Moreover, the reduction conditions are compatible with the presence of a variety of polar functional groups in the substrates, products, and solvents, which are not tolerant under ionic and metal-catalyzed conditions. Carbon-carbon bond formation is possible with use of the carbon-centered radicals that are generated. The results clearly reveal the synthetic utility of arylthiols in organic synthesis.

Dehydration of amides and oximes can be catalysed by 3 A molecular sieves or by tungsten trioxide under flash vacuum pyrolysis (FVP) conditions. This provides a convenient synthesis of aliphatic, aromatic, and heterocyclic nitriles, generally in excellent yields under mild, neutral, and short contact time conditions. Georg Thieme Verlag Stuttgart.

The invention relates to a Rhodococcus polynucleotide cluster which contains nucleotide sequences which encode polypeptides having the activity of a nitrile hydratase, of an auxiliary protein P15K which activates this enzyme and of a cobalt transporter, to transformed microorganisms in which the nucleotide sequences encoding these proteins are present in increased quantity, and to the use of the transformed microorganisms for preparing amides from nitriles.

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.

Thermolyses of seven dialkyl, two alkyl-aryl and two diaryl O-benzyl ketoxime ethers, R1R2C=NOCH2Ph, have been examined in three hydrogen donor solvents: tetralin, 9,10-dihydrophenanthrene, and 9,10-dihydroanthracene. All the oxime ethers gave the products expected from homolytic scission of both the O-C bond (viz., R1R2C=NOH and PhCH3) and N-O bond (viz., R1R2C=NH and PhCH2OH). The yields of these products depended on which solvent was used and the rates of decomposition of the O-benzyl oxime ethers were greater in 9,10-dihydrophenanthrene and 9,10-dihydroanthracene than in tetralin. These results indicated that a reverse radical disproportionation reaction in which a hydrogen atom was transferred from the solvent to the oxime ether, followed by β-scission of the resultant aminoalkyl radical, must be important in the latter two solvents. Benzaldehyde was found to be an additional product from thermolyses conducted in tetralin. This, and other evidence, indicated that another induced decomposition mode involving abstraction of a benzylic hydrogen atom, followed by β-scission of the resulting benzyl radical, became important for some substrates. Participation by minor amounts of enamine tautomers of the oxime ethers was shown to be negligible by comparison of thermolysis data for the O-benzyloxime of bicyclo[3.3.1]nonan-9-one, which cannot give an enamine tautomer, with that of the O-benzyloxime of cyclohexanone.

Dimethyl dithiocarbonate (DMDTC) has been shown to be an efficient dehydrating agent for a range of oximes derived from aliphatic, aromatic and heteroaromatic aldehydes yielding the corresponding nitriles in high yields.

Treatment of an α-amino acid with N-bromosuccinimide in water at pH 5 or in an alcoholic-aqueous ammonium chloride mixture, followed by addition of nickel(II) chloride and sodium borohydride, effected an overall decarboxylation via an intermediate nitrile to afford the corresponding amine in good yield.

3-Phenylpropionitrile was synthesized from Z-3-phenylpropionaldoxime (0.75 M) in a quantitative yield (98 g/l) by the use of cells of Escherichia coli JM 109/pOxD-90F, a transformant harboring a gene for a new enzyme, phenylacetaldoxime dehydratase, from Bacillus sp. strain OxB-1. Other arylalkyl- and alkyl-nitriles were also synthesized in high yields from the corresponding aldoximes. Moreover, 3-phenylpropionitrile was successfully synthesized by the recombinant cells in 70 and 100% yields from 0.1 M unpurified E/Z-3-phenylpropionaldoxime, which is spontaneously formed from 3-phenylpropionaldehyde and hydroxylamine in a butyl acetate/water biphasic system and aqueous phase, respectively.

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.

PCT No. PCT/FR98/01316 Sec. 371 Date Jan. 14, 1999 Sec. 102(e) Date Jan. 14, 1999 PCT Filed Jun. 23, 1998 PCT Pub. No. WO98/58974 PCT Pub. Date Dec. 30, 1998The invention relates to a process for polymerizing block polymers of general formula (I): in which process the following are brought into contact with each other: an ethylenically unsaturated monomer of formula: CYY'(=CW-CW')a=CH2, a precursor compoun of general formula (II): a radical polymerization initiator.

A hydrotalcite-like material, Mg6Al2(OH)16Cl2-xCN x·4H2O (x= 1.53-1.94), was prepared and tested as a reagent for the nucleophilic substitution for chlorine atom of C6H5CH2Cl, C4H9Cl, and C3H7Cl by the CN ions in the interlayer of the material. The corresponding organic cyanides were obtained at 353 K in a non-polar solvent, toluene.

A nitrile compound or an amide compound is hydrolyzed in the presence of an inorganic acid or other acidic catalyst or an alkali metal hydroxide or other basic catalyst, and the by-produced ammonium salt of the acidic catalyst or the produced salt of a carboxylic acid and a base is electrodialysed to form an acid and ammonia or aqueous ammonia, or to form a base and ammonia. The obtained acid or base may be recycled as a catalyst for the hydrolysis of the nitrile compound or amide compound, and the obtained ammonia is reutilized as a nitrogen source for the nitrile compound or amide compound. Such amide compound may be produced by hydration of a nitrite compound in the presence of a manganese oxide.

An investigation of the regioselectivity and mechanisms of the photochemical addition of NH3, PH3, and SiH4 to olefinic and acetylenic nitriles is described. The photolysis of NH3 in the presence of acrylonitrile led to the α-addition product 2-aminopropanenitrile (2), propanenitrile, and 2,3-dimethylbutanedinitrile (3). When NH3 was photolyzed in the presence of substituted derivatives (crotononitrile, methacrylonitrile, or 1-cyclohexenecarbonitrile), the α-addition products were still obtained. However, under similar reaction conditions, only the β-addition products, 7 and 8, were obtained from acrylonitrile and PH3, or acrylonitrile and SiH4, respectively. On the other hand, the photolysis of 2-butynenitrile and NH3 gave the β-addition products, (Z)- and (E)-3-aminocrotononitrile (10). The photolysis of these acetylenic nitriles with PH3 or SiH4 also gave the β-adducts (12) and (13). The α-addition of NH3 proceeds by the stepwise addition of H· and ·NH2, respectively, to the α,β-unsaturated nitriles. The β-addition products are formed by a radical chain mechanism initiated by photochemically generated radicals. The radical chain pathway provides an explanation for a number of previously described photochemical additions to olefins and acetylenes. Photochemical processes similar to the addition of ammonia and phosphine to unsaturated organic compounds may have played a role in the evolution of the atmosphere of the primitive Earth, and may even be currently occurring in the atmospheres of other planets.

A process which comprises contacting and catalytically reacting under essentially anhydrous conditions in the liquid phase an amide with a nitrile according to the equation: where R and R1 are not the same and are each selected from (1) H, hydrocarbyl, a hydrocarbyl group substituted with: one or more of F, Cl, Br, I, amido, cyano, formyl, hydrocarbylcarbonyl, hydrocarbyloxy, hydrocarbyloxycarbonyl, hydrocarbylcarbonyloxy and dihydrocarbylamino, and (2) any of group (1) where one or more H atoms are substituted by a deuterium atom,

Dichlorodicyanomethane reacts readily with oximes, forming the products from addition at one nitrile group.The O-iminoacetyl derivatives of the oximes obtained from ketones and benzaldehyde are stable and can be isolated in the free form.In the case of the oximes of aliphatic aldehydes and furfural the condensation products undergo intramolecular rearrangement, leading to dichlorocyanoacetamide and the corresponding nitriles.The last reaction is a new method for the production of nitriles from aldoximes.

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The dichlorocarbene generation reaction from CHCl3 and solid KOH in CH2Cl2 was catalyzed by the p-t-butylcalixarene derivative 1 which bears six 3,6,9-trioxadecyl substituents on the phenolic oxygens.Dichlorocarbene generated by this method reacted efficiently with alkenes and amides to give dichlorocyclopropane derivatives and nitriles, respectively, in high yields.The reaction with alkadiene having isolated double bonds gave mixtures of the mono- and bis-dichlorocarbene adducts, but the monoadduct formation always predominated.The catalytic action of the calixarene and the reactivity features of dichlorocarbene generated by the above procedure are discussed on the basis of kinetic measurements.They are also compared with those of the 18-crown-6-catalyzed reactions.

The IR data on adsorption and interaction of isobutanol and ammonia on the zinc oxide surface were generalized.A mechanism for the formation of the nitrile group during gas phase ammonolysis of aliphatic alcohols was suggested.

Kinetics of oxidations of several amino acids (AA) (glycine, alanine, valine, leucine and phenylalanine) by dichloramine-B (DCB) have been studied in aquo-methanol (1 : 1, v/v) in the presence of perchloric acid.The reactions show two ranges in .In the first range of (0.0005-0.005 mol dm-3), the oxidations exhibit second order kinetics in , fractional order in and inverse fractional order in +>.In the second range of (0.005-0.10 mol dm-3) also the reactions show similar dependence in , but generally show first order kinetics in and inverse first order in +>.The rates slightly increase with increasing ionic strength, while decrease with increase in methanol composition of the solvent.Addition of benzenesulphonamide, the reduced product of the oxidant, has no significant effect on the rates of oxidations.Suitable mechanisms consistent with the observed results have been considered and the related rate laws deduced.Coefficients of the rate limiting steps have been calculated at different temperatures and the activation parameters corresponding to these constants are also computed.The validity of the mechanisms is tested by recalculating the rate constants from the deduced rate laws as and +> are varied.Reasonably good agreement between the recalculated values and the experimental constants provide support to the proposed mechanisms.

Kinetics of oxidation of several α-amino acids (AA) by dichloramine-B have been studied in aqueous acetic acid in presence of perchloric acid.The rates of oxidations shown two ranges in with zero and inverse fractional order in +>.The reactions generally show second order kinetics in in both the acid ranges and fractional order in , although the magnitudes of the fractional orders are different.Oxidations of some amino acids have also been investigated in the presence of sodium acetate.Under these conditions the rates are independent of .The results indicate the participation of acetate ions in the reaction in addition to the secondary salt effect.Increase in acetic acid composition of the solvent decreases the rates of oxidations.Two-pathway mechanisms consistent with observed results have been considered.The coefficients of the rate-limiting steps at different temperatures and the corresponding activation parameters are also computed.

The hydroformylation of methyl methacrylate (1) or t-butyl methacrylate (2) takes place with fair to good chemoselectivity, the regioselectivity depending on the catalyst precursor used.By contrast, methacrylonitrile (3), methacrylamide (4), and N-benzyl-methacrylamide (5) undergo hydroformylation followed by subsequent reactions.The formyl product formed is reduced to the corresponding 2-cyano-2-methylpropan-1-ol in the case of 3, and undergoes cyclization to 2-methyl-2,3-dehydrobutyrolactames for 4 and 5.Under conditions of hydrocarbalkoxylation in the presence of palladium catalysts, 4 gives 3-methylsuccinimide.In the enantioselective reactions, extents of asymmetric induction of about 20-50percent have been obtained.