- Preparation method of m-methoxyphenethylamine
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The invention discloses a preparation method of m-methoxyethylamine, and relates to the field of organic synthesis preparation chemistry. The preparation method comprises the following steps: adding M-methoxybenzyl chloride to an aqueous solution of cyanide, carrying out cyanation reaction at 60 - 95 °C DEG C, generating M-methoxycyanide, and then cooling and crystallizing in acetone to obtain m-methoxycyanide crystals. A proper amount of ammonia gas is introduced into the solvent, then a proper amount of ammonia gas is introduced, and then hydrogen is introduced to carry out catalytic hydrogenation reaction at a temperature 110 - 160 °C, and the hydrogenated product is distilled under reduced pressure to obtain m-methoxyethylamine. The preparation method of the meta-methoxyethylamine is simple, the raw materials are easily available, the process is easy to control, the cost is low, and the method has the characteristics of high yield, high purity, environmental friendliness and the like, and is suitable for industrial production.
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Paragraph 0017; 0049-0052; 0055-0058; 0061-0064
(2021/11/14)
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- Assembly of α-(Hetero)aryl Nitriles via Copper-Catalyzed Coupling Reactions with (Hetero)aryl Chlorides and Bromides
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α-(Hetero)aryl nitriles are important structural motifs for pharmaceutical design. The known methods for direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination of copper salts and oxalic diamides enables the coupling of a variety of (hetero)aryl halides (Cl, Br) and ethyl cyanoacetate under mild conditions, affording α-(hetero)arylacetonitriles via one-pot decarboxylation. Additionally, the CuBr/oxalic diamide catalyzed coupling of (hetero)aryl bromides with α-alkyl-substituted ethyl cyanoacetates proceeds smoothly at 60 °C, leading to the formation of α-alkyl (hetero)arylacetonitriles after decarboxylation. The method features a general substrate scope and is compatible with various functionalities and heteroaryls.
- Chen, Ying,Xu, Lanting,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 7082 - 7086
(2021/02/26)
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- Crown ether functionalized magnetic hydroxyapatite as eco-friendly microvessel inorganic-organic hybrid nanocatalyst in nucleophilic substitution reactions: an approach to benzyl thiocyanate, cyanide, azide and acetate derivatives
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In this paper, high catalytic activity of 4′,4″-diformyl dibenzo-18-crown-6 anchored onto the functionalized magnetite hydroxyapatite (γ-Fe2O3@HAp–Crown) as a new, versatile and magnetically recoverable catalyst, was prepared. It evaluated as phase-transfer catalyst and molecular host system for nucleophilic substitution reactions of benzyl halides with thiocyanate, cyanide, azide and acetate anions in water. No evidence for the formation of by-products was observed and the products obtained in pure form without further purification. The nanocomposite was easily removed from solution via application of a magnetic field, allowing straightforward recovery and reuse. The synthesized nanocomposite was characterized by several techniques such as FT-IR, TGA-DTG, EDX, XRD, BET, FE-SEM, TEM and VSM.
- Azaroon, Maedeh,Kiasat, Ali Reza
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- Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source
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A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
- Huang, Yubing,Yu, Yue,Zhu, Zhongzhi,Zhu, Chuanle,Cen, Jinghe,Li, Xianwei,Wu, Wanqing,Jiang, Huanfeng
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p. 7621 - 7627
(2017/07/26)
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- Ionic liquid-induced conversion of methoxymethyl-protected alcohols into nitriles and iodides using [Hmim][NO3]
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This Letter reports a one-pot efficient conversion of methoxymethyl-ethers into their corresponding nitriles and iodides using the ionic liquid, 1-methyl-3H-imidazolium nitrate ([Hmim][NO3]) under microwave irradiation. A variety of products were prepared in high yields using this method.
- Noei, Jalil,Mirjafari, Arsalan
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supporting information
p. 4424 - 4426
(2014/08/05)
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- Synthesis of α-aryl esters and nitriles: Deaminative coupling of α-aminoesters and α-aminoacetonitriles with arylboronic acids
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Transition-metal-free synthesis of α-aryl esters and nitriles using arylboronic acids with α-aminoesters and α-aminoacetonitriles, respectively, as the starting materials has been developed. The reaction represents a rare case of converting C(sp3)-N bonds into C(sp3)-C(sp2) bonds. The reaction conditions are mild, demonstrate good functional-group tolerance, and can be scaled up. Touch base: A transition-metal-free protocol for the synthesis of α-aryl esters and nitriles by deaminative coupling is presented. Strong bases and transition-metal catalysts are not needed. The new synthetic method uses readily available starting materials and demonstrates wide substrate scope.
- Wu, Guojiao,Deng, Yifan,Wu, Chaoqiang,Zhang, Yan,Wang, Jianbo
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supporting information
p. 10510 - 10514
(2016/02/18)
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- One-pot synthesis of nitriles from aldehydes catalyzed by deep eutectic solvent
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The choline chloride-urea (1:2) based deep eutectic mixture as an efficient and ecofriendly catalyst for the one-pot synthesis of nitriles from aldehydes under solvent-free conditions under both conventional and microwave irradiation; the products were obtained in good to excellent yields. Georg Thieme Verlag Stuttgart New York.
- Patil, Umakant B.,Shendage, Suresh S.,Nagarkar, Jayashree M.
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p. 3295 - 3299
(2013/12/04)
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- A heterogeneous palladium catalyst hybridised with a titanium dioxide photocatalyst for direct C-C bond formation between an aromatic ring and acetonitrile
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A palladium catalyst hybridised with a titanium dioxide photocatalyst can promote cyanomethylation of an aromatic ring by using acetonitrile, where the photocatalyst activates acetonitrile to form a cyanomethyl radical before the C-C bond formation using the palladium catalyst.
- Yoshida, Hisao,Fujimura, Yuki,Yuzawa, Hayato,Kumagai, Jun,Yoshida, Tomoko
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supporting information
p. 3793 - 3795
(2013/05/22)
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- Magnetic nanoparticles grafted with β-cyclodextrin-polyurethane polymer as a novel nanomagnetic polymer brush catalyst for nucleophilic substitution reactions of benzyl halides in water
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The polymer coated magnetic nanoparticles has gained significant attention for potential applications in biomedicine, separations, and magnetic storage. In this study, β-cyclodextrin-polyurethane polymer coated Fe 3O4 magnetic nanoparticle as a novel class of hybrid organic/inorganic molecular catalyst was successfully prepared and evaluated as solid-liquid phase-transfer catalyst and molecular host system for nucleophilic substitution reactions. The nanocomposite has demonstrated the ability to catalytic the nucleophilic substitution reaction of benzyl halides with thiocyanate, azide, cyanide and acetate anions in water. No evidence for the formation of by-products for example isothiocyanate or alcohol was observed and the products obtained in pure form without further purification. The nanomagnetic polymer brush catalyst was easily removed from solution via application of a magnetic field, allowing straightforward recovery and reuse. Results obtained from scanning electron microscopy (SEM) and vibrating sample magnetometery (VSM) show that the synthesized magnetic nanocomposite are superparamagnetic with a mean diameter of 59 nm. The grafting of β-cyclodextrin-polyurethane polymer to Fe3O4 magnetic nanoparticle is confirmed by Fourier transform infrared spectroscopy (FT-IR).
- Kiasat, Ali Reza,Nazari, Simin
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- Antimicrobial volatile glucosinolate autolysis products from Hornungia petraea (L.) Rchb. (Brassicaceae)
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Plant samples of Hornungia petraea were analyzed for glucosinolate (GLS) autolysis metabolites for the first time. GC-MS analysis of the autolysate and the synthesis of a series (12 compounds) of possible glucosinolate breakdown products revealed/corroborated the presence of glucoaubrietin, glucolimnanthin, glucolepigramin and glucotropaeolin in this species as the most likely "mustard oil" precursors. GLS degradation products identified in the autolysate of H. petraea, benzyl isothiocyanate, 3- and 4-methoxybenzyl isothiocyanate, along with several other structurally related compounds were evaluated for antimicrobial activity in order to possibly pinpoint the role of the latter secondary metabolites in the plant tissues. The assays showed a very high antibacterial activity of the tested isothiocyanates against Sarcina lutea and an antifungal effect against Aspergillus fumigatus and Candida albicans with MIC values in the order of 1 μg/ml value.
- Radulovi?, Niko S.,Deki?, Milan S.,Stojanovi?-Radi?, Zorica Z.
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experimental part
p. 351 - 357
(2012/07/16)
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- Application of β-cyclodextrin-polyurethane as a stationary microvessel and solid-liquid phase-transfer catalyst: Preparation of benzyl cyanides and azides in water
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Application of water tolerant heterogeneous catalyst, β-cyclodextrin- polyurethane (β-CDPU) polymer, as an efficient microvessel and polymeric host system for nucleophilic substitution reaction of benzyl halides with cyanide and azide anions in water has been described. The reactions gave only pure products, which did not require any further purification. The most important features of this method are high yields, clean reactions and that the catalyst can be recovered and recycled.
- Kiasat, Ali Reza,Nazari, Simin
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p. 102 - 105
(2013/01/15)
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- Rhodium-catalyzed asymmetric hydrogenation of olefins with PhthalaPhos, a new class of chiral supramolecular ligands
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A library of 19 binol-derived chiral monophosphites that contain a phthalic acid diamide group (Phthala- Phos) has been designed and synthesized in four steps. These new ligands were screened in the rhodium-catalyzed enantioselective hydrogenation of prochiral dehydroamino esters and enamides. Several members of the library showed excellent enantioselectivity with methyl 2-acetamido acrylate (6 ligands gave >97% ee), methyl (Z)-2- acetamido cinnamate (6 ligands gave >94% ee), and N-(1-phenylvinyl)acetamide (9 ligands gave >95% ee), whilst only a few representatives afforded high enantioselectivities for challenging and industrially relevant substrates N-(3,4-dihydronaphthalen-1- yl)-acetamide (96% ee in one case) and methyl (E)-2-(acetamidomethyl)-3- phenylacrylate (99% ee in one case). In most cases, the new ligands were more active and more stereoselective than their structurally related monodentate phosphites (which are devoid of functional groups that are capable of hydrogen-bonding interactions). Control experiments and kinetic studies were carried out that allowed us to demonstrate that hydrogen-bonding interactions involving the diamide group of the PhthalaPhos ligands strongly contribute to their outstanding catalytic properties. Computational studies carried out on a rhodium precatalyst and on a conceivable intermediate in the hydrogenation catalytic cycle shed some light on the role played by hydrogen bonding, which is likely to act in a substrate-orientation effect.
- Pignataro, Luca,Boghi, Michele,Civera, Monica,Carboni, Stefano,Piarulli, Umberto,Gennari, Cesare
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p. 1383 - 1400
(2012/03/27)
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- Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
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Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright
- Shang, Rui,Ji, Dong-Sheng,Chu, Ling,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 4470 - 4474
(2011/06/24)
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- Microwave-promoted, one-pot conversion of alkoxymethylated protected alcohols into their corresponding nitriles, bromides, and iodides using [bmim][InCl4] as a green catalyst
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The Lewis acid room temperature ionic liquid, [bmim][InCl4], was found to be an efficient and green catalyst for the highly chemoselective and one-pot conversion of MOM- or EOM-ethers into their corresponding nitriles, bromides, and iodides under microwave irradiation. The procedures are simple, rapid, and high yielding. The catalyst exhibited a remarkable reactivity and is reusable.
- Mirjafari, Arsalan,Mohammadpoor-Baltork, Iraj,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza
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supporting information; experimental part
p. 3274 - 3276
(2010/07/18)
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- TRICYCLIC INHIBITORS OF 5-LIPOXYGENASE
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Described herein are compounds and pharmaceutical compositions containing such compounds, which inhibit the activity of 5-lipoxygenase (5-LO). Also described herein are methods of using such 5-LO inhibitors, alone and in combination with other compounds, for treating respiratory, cardiovascular, and other leukotriene-dependent or leukotriene mediated conditions, diseases, or disorders.
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Page/Page column 85; 86
(2010/11/28)
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- 3-methoxybenzyl thiourea derivatives and improved lipid compositions containing same
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1-(3-methoxybenzyl)-3-substituted thiourea antioxidant compounds and improved lipids compositions which are supplemented with amounts of such antioxidant compounds effective for augmenting oxidative stability of the base lipid are provided. Also provided are methods for enhancing the oxidative stability of a lipid comprising supplementing a base lipid in need of enhanced oxidative stability with at least one 1-(3-methoxybenzyl)-3-substituted thiourea compound of the present invention.
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- 3-O-Substituted benzyl pyridazinone derivatives as COX inhibitors
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New 3-O-substituted benzyl pyridazinone compounds have been synthesised and evaluated for their cyclooxygenase inhibitory activity and COX-2 selectivity. Among the compounds synthesised, three compounds (11b-11d) have shown in vitro COX-2 selectivity. These compounds have been evaluated for their in vivo potential using carrageenan-induced rat paw edema assay. One compound (11b) showed 32% anti-inflammatory activity at 30 mg kg-1 dose.
- Chintakunta, Vamsee Krishna,Akella, Venkateswarlu,Vedula, Manohar Sharma,Mamnoor, Prem Kumar,Mishra, Parimal,Casturi, Seshagiri Rao,Vangoori, Akhila,Rajagopalan, Ramanujam
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p. 339 - 347
(2007/10/03)
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- Design, synthesis and antiproliferative activity of tripentones: A new series of antitubulin agents
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Structure-activity relationship studies of a new series of tripentones (thieno[2,3-b]pyrrolizin-8-ones), led us to prepare several derivatives with antiproliferative activities. The most promising 3-(3-hydroxy-4-methoxyphenyl)thieno[2,3-b]pyrrolizin-8-one 20 (leukemia L1210, IC50 = 15 nM) was shown to be a potent inhibitor of tubulin polymerization.
- Lisowski, Vincent,Enguehard, Cecile,Lancelot, Jean-Charles,Caignard, Daniel-Henri,Lambel, Stephanie,Leonce, Stephane,Pierre, Alain,Atassi, Ghanem,Renard, Pierre,Rault, Sylvain
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p. 2205 - 2208
(2007/10/03)
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- Carboanion Reactivity: Kinetics of the Reactions of Benzyl Cyanide Anions with Aromatic Nitro-compounds
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Rate and equilibrium measurements are reported for the reactions in methanol of carbanions derived from 12 ring-substituted benzyl cyanides with 1,3,5-trinitrobenzene to give ?-adducts.Some data for reaction of the carbanions with 4-nitrobenzofuroxan were also measured.With increasing carbanion reactivity, rate constants approach a limit of just below 109 dm3 mol-1 s-1.Intrinsic reactivities of carbanions in ?-adduct forming reactions and in proton transfer reactions are compared.
- Atherton, John H.,Crampton, Michael R.,Duffield, Gaynor L.,Stevens, J. Andrew
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p. 443 - 448
(2007/10/02)
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- The Acidity of Weak Carbon Acids. Part 3. The Kinetic Acidities of Substituted Benzyl Cyanides using Secondary Aliphatic Amines and Guanidines as Bases
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The rate coefficients for the base-catalysed detritiation of a series of m-substituted benzyl cyanides in DMSO and methanol have been measured at 25.0 deg C.In DMSO the bases are a series of secondary aliphatic amines and guanidines and in methanolic methoxide.For benzyl cyanide and piperidine in DMSO, the rate coefficients for detritiation at 55.0 deg C and dedeuteration at 25.0 deg C were also measured.The kinetic isotope effect and activation parameters indicate the rate determining step to be the ionisation process.Broensted coefficients, α and δ, have been calculated from both the known pKa values of the substrates and measured pKa values of the bases in DMSO.Both indicate a transition state composed of an "advanced" carbanionic structure.There is no reactivity-selectivity relationship apparent.The results are discussed in relation to Marcus and related theories.
- Bowden, Keith,Madvi, Nighat S.,Ranson, Richard J.
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p. 2474 - 2496
(2007/10/02)
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- ARYNIC CONDENSATION OF NITRILE ANIONS IN THE PRESENCE OF THE COMPLEX BASE NaNH2-CH3CH2(OCH2CH2)2ONa
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Nitrile anions are easily condensed with aryl halides in the presence of Complex Base NaNH2-CH3CH2(OCH2CH2)2ONa via the intermediate arynes.
- Carre, M. C.,Ezzinadi, A. S.,Zouaoui, M. A.,Geoffroy, P.,Caubere, P.
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p. 3323 - 3330
(2007/10/02)
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- ANTIULCER BENZIMIDAZOLE DERIVATIVES
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Compounds of formula I STR1 in which R 1 and R 2, which may be the same or different, are hydrogen, a C 1 to C 3 alkyl group or R 1 and R 2 together with the nitrogen to which they are attached form an optionally substituted heterocyclic ring; R 3 and R. sub.4, which may be the same or different are hydrogen, a C 1 to C. sub.3 alkyl or an optionally substituted C 3 to C 6 cycloalkyl group, or R 3 and R 4 together with the nitrogen to which they are attached form an optionally substituted heterocyclic ring; m is 0, 1 or 2; p is 0, 1 or 2; E is an alkylene group connected to or interrupted by an oxygen or a sulphur atom; J is hydrogen or a substituent group; and their pharmaceutically acceptable salts have utility as histamine H 2-receptor antagonists.
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- Photochemical Aromatic Cyanomethylation: Aromatic Substitution by Way of Radical Cations
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Photolysis at 254 nm of chloroacetonitrile in the presence of aromatic hydrocarbons led to ring cyanomethylation.In addition radical coupling products were found, especially with toluene where 3-phenylpropionitrile, succinonitrile, and bibenzyl accompanied the tolylacetonitriles.These same byproducts were obtained from toluene and chloroacetonitrile upon thermolysis with peroxide initiators, but no nuclear cyanomethylation was observed.The mechanism for aromatic cyanomethylation involves initial excitation of the aromatic hydrocarbons, followed by an electron transfer (probably by way of an exiplex) to chloroacetonitrile, which was found to quench aromatic fluorescence at high rates.Direct spectral evidence for the resulting radical cation with p-dimethoxybenzen was obtained by using flash laser spectroscopy.Loss of a chloride ion from the resulting radical anion produces a cyanomethyl radical in close proximity to an aromatic radical cation.Coupling leads to the aromatic substitution products whereas radicals escaping from the cage account for the observed byproducts.
- Kurz, M. E.,Lapin, S. C.,Miriam, K.,Hagen, T. J.,Qian, X. Q.
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p. 2728 - 2733
(2007/10/02)
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- Photochemical Aromatic Cyanomethylation
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Cyanomethylation is accomplished by the photolysis of chloroacetonitrile in the presence of aromatics by way of electron transfer followed by radical coupling.
- Lapin, Stephen,Kurz, Michael E.
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p. 817 - 818
(2007/10/02)
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