- Electrochemical Tandem Olefination and Hydrogenation Reaction with Ammonia
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An electrochemical Horner-Wadsworth-Emmons/hydrogenation tandem reaction was achieved using ammonia as electron and proton donors. The reaction could give two-carbon-elongated ester and nitrile from aldehyde or ketones directly. This reaction could proceed with a catalytic amount of base or even without a base. The ammonia provides both the electron and proton for this tandem reaction and enables the catalyst-free hydrogenation of an α,β-unsaturated HWE intermediate. More than 40 examples were reported, and functional groups, including heterocycles and hydroxyl, were tolerated.
- Zhang, Xiaofeng,Jiang, Runze,Cheng, Xu
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p. 16016 - 16025
(2021/08/24)
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- MITOCHONDRIA-TARGETING PEPTIDES
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Disclosed are non-natural peptides useful for the treatment and prevention of ischemia-reperfusion injury (e.g., cardiac ischemia-reperfusion injury) or myocardial infarction.
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0153; 0154; 0155; 0162; 0163
(2018/05/07)
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- Formal reductive addition of acetonitrile to aldehydes and ketones
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An efficient and highly productive rhodium-catalyzed method for the synthesis of nitriles employing aldehydes or ketones, methyl cyanoacetate, water and carbon monoxide as starting materials has been developed. Simple rhodium chloride without any ligands can be used. The fine tuning of the substrate can lead to the activity higher than 5000 TON.
- Muratov, Karim,Kuchuk, Ekaterina,Vellalath, Sreekumar,Afanasyev, Oleg I.,Moskovets, Alexei P.,Denisov, Gleb,Chusov, Denis
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supporting information
p. 7693 - 7701
(2018/11/02)
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- A mineralogically-inspired silver-bismuth hybrid material: An efficient heterogeneous catalyst for the direct synthesis of nitriles from terminal alkynes
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The synthesis and characterization of a silver-containing hybrid material is reported as a novel heterogeneous noble metal catalyst. In order to eliminate the need for traditional immobilization techniques, and to create a solid material with structurally-bound silver catalytic centers, the layered structure of a naturally occurring mineral served as the basis of the initial catalyst design. The novel material was prepared by means of the urea-mediated homogeneous precipitation of the corresponding metal nitrates, and was fully characterized by means of diverse instrumental techniques (X-ray diffractometry, Raman, IR, UV-Vis, EPR, X-ray photoelectron spectroscopies, thermal methods as well as atomic force, scanning and transmission electron microscopies). The as-prepared material exhibited outstanding activity in silver-catalyzed CC bond activation to yield organic nitriles directly from terminal alkynes with less environmental concerns as compared to the classical synthesis methods. The effects of the reaction time, the temperature, as well as the role of various solvents, nitrogen sources and additives were carefully scrutinized in order to achieve high-yielding and selective nitrile formation. The heterogeneous nature of the reaction was verified and the solid catalyst was recycled and reused numerous times without loss of its activity or degradation of its structure, thereby offering a sustainable synthetic methodology.
- ?tv?s, Sándor B.,Mészáros, Rebeka,Varga, Gábor,Kocsis, Marianna,Kónya, Zoltán,Kukovecz, ákos,Pusztai, Péter,Sipos, Pál,Pálinkó, István,Fül?p, Ferenc
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p. 1007 - 1019
(2018/03/13)
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- One-Pot Preparation of C1-Homologated Aliphatic Nitriles from Aldehydes through a Wittig Reaction under Metal-Cyanide-Free Conditions
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A one-pot protocol to obtain C1-homologated aliphatic nitriles was achieved by treating aromatic and aliphatic aldehydes with the (methoxymethyl)triphenylphosphonium ylide followed by hydrolysis of the resulting methyl vinyl ethers with pTsOH (Ts = para-toluenesulfonyl) and treatment with molecular iodine and aqueous ammonia under metal cyanide free conditions. Neopentyl-type nitriles, which could not be obtained by conventional methods that involved conversion of the neopentyl alcohol into a tosylate and treatment with metal cyanide, were successfully obtained by using the present method.
- Ezawa, Masatoshi,Togo, Hideo
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p. 2379 - 2384
(2017/05/01)
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- Direct cyanomethylation of aliphatic and aromatic hydrocarbons with acetonitrile over a metal loaded titanium oxide photocatalyst
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A platinum-loaded TiO2 (Pt/TiO2) photocatalyst promoted cyanomethylation of aliphatic hydrocarbons, namely cyclohexane and cyclohexene, with acetonitrile, where the photogenerated hole oxidatively dissociates the C-H bond of both the acetonitrile and the aliphatic hydrocarbons to form each corresponding radical species before their radical cross-coupling. The Pt/TiO2 photocatalyst was more active than the Pd/TiO2 photocatalyst in these reactions. In contrast, the cyanomethylation of benzene was promoted by the Pd/TiO2 photocatalyst or a physical mixture of the Pt/TiO2 photocatalyst and a Pd catalyst supported by Al2O3, while it was hardly promoted by the Pt/TiO2 photocatalyst alone. The temperature dependence of the reaction rate proved that the Pd nanoparticles on the TiO2 photocatalyst thermally function as a metal catalyst. These results clearly suggest that the Pd metal catalyst is necessary for the cyanomethylation of benzene. However, in the cyanomethylation of aliphatic hydrocarbons, the catalytic effect of the metal particles was not observed, meaning that the radical coupling takes place without the metal catalysis. Thus, it is concluded that in the case of the benzene cyanomethylation the Pd nanoparticles play dual roles, as a catalyst to catalyse the substitution reaction of benzene with the cyanomethyl radical, and as an electron receiver to reduce the recombination of the photoexcited electrons and holes in the TiO2 photocatalyst, although they could not contribute as a catalyst to the cyanomethylation of aliphatic hydrocarbons.
- Wada, Emiko,Takeuchi, Tomoaki,Fujimura, Yuki,Tyagi, Akanksha,Kato, Tatsuhisa,Yoshida, Hisao
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p. 2457 - 2466
(2017/07/22)
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- TETRAAZAPORPHYRIN COMPOUND, COLOR CORRECTION FILTER AND EXTERNAL LIGHT CORRECTION FILTER
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PROBLEM TO BE SOLVED: To provide a tetraazaporphyrin compound excellent in light resistance, and a color correction filter and an external light correction filter containing the same. SOLUTION: There is provided a tetraazaporphyrin compound which is a mixture of 4 kinds of isomers obtained by heat cyclization reaction of a metal or a metal derivative with a cis body of 1,2-dicyanoethylene compound represented by the following formula (6) (4 molar) in an alcohol solvent the coexistence of an organic basic. In the formula (6), one of two substitutions Z1 and Z2 is a cyclic alkyl group which may have a substituent and the other is an aryl group which may have a substituent. COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0046
(2016/11/21)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
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- Iridium-catalyzed α-alkylation of acetonitrile with primary and secondary alcohols
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Acetonitrile is successfully alkylated with primary and secondary alcohols in the presence of t-BuOK using [Ir(OH)- (cod)]2 as a catalyst. This method provides a very clean and atom-economical convenient direct route to substituted nitriles, which are very important raw materials in organic and industrial chemistry.
- Sawaguchi, Takuya,Obora, Yasushi
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supporting information; experimental part
p. 1055 - 1057
(2011/12/05)
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- Precision polyethylene: Changes in morphology as a function of alkyl branch size
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Metathesis polycondensation chemistry has been employed to control the crystalline morphology of a series of 11 precision-branched polyethylene structures, the branch being placed on each 21st carbon and ranging in size from a methyl group to an adamantyl group. The crystalline unit cell is shifted from orthorhombic to triclinic, depending upon the nature of the precision branch. Further, the branch can be positioned either in the crystalline phase or in the amorphous phase of polyethylene, a morphology change dictated by the size of the precision branch. This level of morphology control is accomplished using step polymerization chemistry to produce polyethylene rather than conventional chain polymerization techniques. Doing so requires the synthesis of a series of unique symmetrical diene monomers incorporating the branch in question, followed by ADMET polymerization and hydrogenation to yield the precision-branched polyethylene under study. Exhaustive structure characterization of all reaction intermediates as well as the precision polymers themselves is presented. A clear change in morphology was observed for such polymers, where small branches (methyl and ethyl) are included in the unit cell, while branches equal to or greater in mass than propyl are excluded from the crystal. When the branch is excluded from the unit cell, all such polyethylene polymers possess essentially the same melting temperature, regardless of the size of the branch, even for the adamantyl branch.
- Rojas, Giovanni,Inci, Bora,Wei, Yuying,Wagener, Kenneth B.
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supporting information; scheme or table
p. 17376 - 17386
(2010/03/23)
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- Photochemistry of N-acetyl-, N-trifluoroacetyl-, N- mesyl-, and N-tosyldibenzothiophene sulfilimines
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(Chemical Equation Presented) Time-resolved infrared (TRIR) spectroscopy, product studies, and computational methods were applied to the photolysis of sulfilimines derived from dibenzothiophene that were expected to release acetylnitrene, trifluoroacetylnitrene, mesylnitrene, and tosylnitrene. All three methods provided results for acetylnitrene consistent with literature precedent and analogous experiments with the benzoylnitrene precursor, i.e., that the ground-state multiplicity is singlet. In contrast, product studies clearly indicate triplet reactivity for trifluoroacetylnitrene, though TRIR experiments were more ambiguous. Product studies suggest that these sulfilimines are superior sources for sulfonylnitrenes, which have triplet grounds states, to the corresponding azides, and computational studies shed light on the electronic structure of the nitrenes.
- Desikan, Vasumathi,Liu, Yonglin,Toscano, John P.,Jenks, William S.
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p. 4398 - 4414
(2008/09/21)
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- Highly efficient conjugate reduction of α,β-unsaturated nitriles catalyzed by copper/xanthene-type bisphosphine complexes
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α,β-Unsaturated nitriles are chemoselectively reduced to the corresponding saturated nitriles in high yields using a copper-DPEphos or Xantphos complex as catalyst in the presence of polymethylhydrosiloxane (PMHS) as the stoichiometric reducing agent and t-butanol as additive. The Royal Society of Chemistry 2005.
- Kim, Daesung,Park, Bu-Mahn,Yun, Jaesook
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p. 1755 - 1757
(2007/10/03)
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- Structure-selectivity relationship in the chemoselective hydrogenation of unsaturated nitriles
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Several unsaturated nitriles of various structures (cinnamonitrile, cyclohex-1-enyl-acetonitrile, acrylonitrile, 3,3-dimethyl-acrylonitrile, geranylnitrile, and 2- and 3-pentenenitrile) with different substituents at the double bond were hydrogenated over
- Kukula, Pavel,Koprivova, Klara
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p. 161 - 171
(2007/10/03)
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- Anti-viral method
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PCT No. PCT/US97/07431 Sec. 371 Date Jan. 6, 1999 Sec. 102(e) Date Jan. 6, 1999 PCT Filed May 2, 1997 PCT Pub. No. WO97/41846 PCT Pub. Date Nov. 13, 1997The present invention provides compounds which inhibit an envelope virus by inhibiting the fusion of the virus with the host cell. The virus may be inhibited in an infected cell, a cell susceptible of infection or a mammal in need thereof.
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- Cathodic behaviour of 1-cycloalken-1-yl phenyl sulfones. I. Competition among dimerization, cleavage, isomerization and oligomerization processes in aprotic media
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1-Cycloalken-1-yl phenyl sulfones 1a and 1b have been studied electrochemically in aprotic media (N,N-dimethylformamide, dimethyl sulfoxide, or acetonitrile containing tetraalkylammonium salts) at a mercury electrode. Their behaviour has been compared with that of 2-norbornen-2-yl phenyl sulfone 1c. The expected cleavage reaction is accompanied by a concomitant isomerization process into allyl sulfones that is triggered by electrogenerated bases. A quantitative determination of the product distribution during controlled-potential electrolyses suggests the formation of dimers and oligomeric species, arising through a Michael addition of the sulfone anions to the activated double bond of these sulfones.
- Prigent, Sylvie,Cauliez, Pascal,Simonet, Jacques,Peters, Dennis G.
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p. 892 - 900
(2007/10/03)
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- Urea, thiourea and guanidine compounds and their use as anti-viral agents
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The present invention provides compounds which inhibit an envelope virus by inhibiting the fusion of the virus with the host cell. The virus may be inhibited in an infected cell, a cell susceptible of infection or a mammal in need thereof.
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- The reduction of α,β-unsaturated nitriles and α-halonitriles with sodium hydrogen telluride
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Sodium hydrogen telluride reacts chemoselectively with α,β- unsaturated nitriles and α-halonitriles linked to aromatic and aliphatic substituents to corresponding saturated nitriles with good yields.
- Blay, Gonzalo,Cardona, Luz,Garcia, Begona,Lahoz, Luisa,Pedro, Jose R.
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p. 8611 - 8618
(2007/10/03)
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- Facile synthesis of nitriles from primary nitro compounds via nitrolic acids and their esters
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The reactions of alkane- and arylalkanenitrolic acids esters Bu3SnH in the presence of a catalytic amount of AIBN in refluxing benzene afforded the corresponding nitriles in excellent yields.
- Chang, Rae Kyu,Kim, Kyongtae
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p. 7791 - 7794
(2007/10/03)
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- Electrochemical Oxidation of Acylsilanes and Their Tosylhydrazones
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Oxidation potentials of acylsilanes were found to be much less positive than those of ketones and aldehydes.The effect of silicon is attributed to the rise of the HOMO level by the interaction between the C-Si ? orbital and the nonbonding p orbital of the carbonyl oxygen which in turn favors the electron transfer.Preparative electrochemical oxidation of acylsilanes proceeded smoothly, giving rise to facile cleavage of the C-Si bond and the introduction of nucleophiles such as alcohols, water, and carbamates onto the carbonyl carbon.Electrochemical properties of tosylhydrazones of acylsilanes were also investigated.A decrease in oxidation potential of tosylhydrazones caused by silyl substitution was found to be smaller than that for carbonyl compounds.Preparative electrochemical oxidation of tosylhydrazones of acylsilanes gave the corresponding nitriles with consumption of a catalytic amount of electricity.
- Yoshida, Jun-ichi,Itoh, Masanori,Matsunaga, Shin-ichiro,Isoe, Sachihiko
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p. 4877 - 4882
(2007/10/02)
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- Synthesis and antiallergy activity of [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one derivatives. II. 6-Alkyl- and 6-cycloalkylalkyl derivatives
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A series of 6-alkyl- or 6-(cycloalkylalkyl)-[1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyr imidin-9(3H)-ones 1b-o was synthesized from the corresponding 1,3,4-thiadiazol-5-amines 3b-o and the antiallergic activities of the products were evaluated. Among the compounds 6-(2-cyclohexylethyl)-[1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]p yrimidin-9(3H)-one 1h, whose X-ray crystallographic stereostructure is shown, was found to be a promising new antiallergic agent, which has low toxicity and dual activity as a leukotriene D4 receptor antagonist and as an orally active mast cell stabilizer.
- Yokohama,Miwa,Aibara,Fujiwara,Matsumoto,Nakayama,Iwamoto,Mori,Moroi,Tsukada,Isoda
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p. 2391 - 2398
(2007/10/02)
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- Light-mediated Cyanomethylation of Cycloalkenes with Acetonitrile
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Addition of cyanomethyl radicals generated from acetonitrile involving initiation by photoinduced decomposition of hydrogen peroxide, to cycloalkenes has been achieved; a method for the synthesis of two homologous nitriles is first reported.
- Sonawane, Harikisan R.,Bellur, Nanjundiah S.,Shah, Virendra G.
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p. 1603 - 1605
(2007/10/02)
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- Novel substituted 3H-1,2,3,5-oxathiadiazole 2-oxides useful as anthihyperglycemic agents
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This invention relates to novel substituted 3H-1,2,3,5-oxathiadiazole 2-oxides, to the processes for their preparation, to methods for using the compounds, and to pharmaceutical compositions thereof. The compounds have pharmaceutical properties which render them beneficial for the treatment of diabetes mellitus and associated conditions.
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- A New Facile Route to Primary Alkanenitriles from Terminal Alkenes via a Hydroboration-Cyanation Sequence
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Terminal alkenes are converted into one-carbon homologated primary alkanenitriles in high yields via hydroboration followed by a reaction with copper(I) cyanide, copper(II) acetate, and copper(II) acetylacetonate.
- Masuda, Yuzuru,Hoshi, Masayuki,Arase, Akira
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p. 266 - 267
(2007/10/02)
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- Conversions of Carbonyl Compounds via Their Polymeric Sulfonylhydrazones into Alkenes, Alkanes, and Nitriles
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Resins consisting of cross-linked poly(styrene-divinylbenzene) matrices functionalized with hydrazinosulfonyl groups react with aldehydes and ketones to form the sulfonylhydrazone derivatives.The extent of the reaction is sensitive to the type of resin and the bulk of the carbonyl compound.When heated strongly under alkaline conditions, the sulfonylhydrazones release the corresponding alkenes; upon the NaBH4 or LiAlH4 treatment, they also release the corresponding alkanes; and, upon refluxing in methanol with potassium cyanide, they release nitriles containing one additional carbon atom.
- Kamogawa, Hiroyoshi,Kanzawa, Asami,Kadoya, Masahiro,Naito, Takeshi,Nanasawa, Masato
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p. 762 - 765
(2007/10/02)
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- Electron-transfer Processes: Metal Salt Catalysed Oxidation of Olefins by Peroxydisulphate
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The reaction of simple olefins (oct-1-ene, oct-2-ene, cyclohexene, cycloheptene) with peroxydisulphate has been investigated under several conditions: (i) in aqueous medium and catalysis by AgI, FeII, and CuII; (ii) in acetic madium and catalysis by CuII, FeIII; (iii) in the presence of traps of nucleophilic alkyl radicals (protonated heteroaromatic bases and 1,4-benzoquinone either in water or in acetic acid).The catalyst and the radical trap govern the selectivity and allow a variety of new synthetic achievements.Evidence for a unified initial mechanism of electron transfer with formation of a radical cation from the olefin is reported to explain all the results.In water the radical cation gives a β-hydroxyalkyl radical, which, depending on the nature of the catalyst and the trap, can give the corresponding saturated alcohol by hydrogen abstraction, the products of CuII oxidation, or β-hydroxyalkylation of the heteroaromatic compound or 1,4-benzoquinone.In acetic acid the radical cation gives a β-acetoxyalkyl radical, which is oxidized to the corresponding allylic acetate by copper(II) acetate or trapped by the heteroaromatic base.
- Arnoldi, Claudio,Citterio, Attilio,Minisci, Francesco
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p. 531 - 542
(2007/10/02)
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- Metal Ion Photoinitiated Addition of Acetonitrile and Methanol to Olefins
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Irradiation of norbornene and silver or thallium trifluoromethanesulfonate in acetonitrile solutions results in the efficient formation of exo-2-(cyanomethyl)bicycloheptane.Investigation of the scope of this reaction established that (a) copper(I or II) salts are not effective, (b) propionitrile and methanol give analogous norbornene-solvent adducts, and (c) acetonitrile addition is observed for several cyclic and acyclic olefins.Investigation of the mechanism of solvent addition indicates that the reaction is initiated by photoinduced electron transfer to silver(I) from coordinated norbornene.Reaction of the resulting norbonene cation radical with acetonitrile yields norbornyl cation and cyanomethyl radical.Free-radical chain addition of the cyanomethyl radical to norbornene then leads to product formation.In ethereal solvents, metal ion catalyzed photodimerization of norbornene has previously been reported for copper(I) salts.This reaction can also be effected by copper(II) and silver(I) salts, but not by Tl(I) salts.
- Bruno, Joseph W.,Marks, Tobin J.,Lewis, Frederick D.
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p. 5580 - 5585
(2007/10/02)
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- Reactions of Acetonitrile in a Radiofrequency Discharge
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Acetonitrile was flowed through an inductively coupled radiofrequency (rf) discharge.The products formed under various conditions of power and flow rate were isolated and quantitated by using gas chromatography.The major products were propionitrile, ethane, and hydrogen cyanide.Reaction of mixtures of acetonitrile and cyclohexane gave these three products and cyanocyclohexylmethane, methylcyclohexane, and cyclohexene.All six products can be rationalized by neutral radical reactions.Emission spectroscopy on acetonitrile plasmas showed the expected CN bands from the excited A2? and B2Σ+ states.Analysis of the peak intensities gave a vibrational temperature of ca. 5900K and a rotational temperature of ca. 735K for B2Σ+ state.Lower power, higher pressure, or added ethane diminished the emission intensity but did not change these temperatures.Added argon had no effect up to a mole fraction of argon of 0.8.The absence of cyanoalkanes from plasmas containing CN and alkyl radicals is noted.
- So, Ying-Hung,Bezuk, Steve J.,Miller, Lary L.
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p. 1475 - 1479
(2007/10/02)
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- Direct One-Step Conversion of Alcohols into Nitriles
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Alcohols are converted into nitriles in good to excellent yields by treatment with 2 equiv of NaCN/Me3SiCl and a catalytic amount of NaI in DMF/CH3CN.
- Davis, Roman,Untch, Karl G.
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p. 2985 - 2987
(2007/10/02)
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- The Conversion of Aldehydes and Ketones via their 2,4,6-Tri-isopropylbenzenesulphonyl Hydrazones into Nitriles containing One Additional Carbon Atom
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2,4,6-Tri-isopropylbenzenesulphonyl hydrazones of aliphatic and alicyclic aldehydes and ketones react readily with potassium cyanide in boiling methanol solution to give the corresponding nitriles (containing one more carbon atom than the original aldehyde or ketone) in satisfactory yield. Under the same conditions, benzaldehyde 2,4,6-tri-isopropylbenzenesulphonyl hydrazone gives phenylacetonitrile in very low yield.In some cases, the arenesulphonyl hydrazones may be generated in situ, in methanol solution, from the carbonyl compounds and 2,4,6-tri-isopropylbenzenesulphonohydrazide (11a), thereby constituting a one-pot preparation or the nitriles.
- Jiricny, Josef,Orere, Daniel M.,Reese, Colin B.
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p. 1487 - 1492
(2007/10/02)
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