- Polyfunctionalized Cage Compounds by Pericyclic Domino Processes of 4,5-Dicyanopyridazine with Dienes: Applications and Limits
-
The title compound 1 was found to behave as an attractive masked bis-diene to give 4-oxatricyclo-[4.3.1.03,7]dec-8-ene, 5-aza- and 5-silatricyclo[5.3.1.03,8]undec-9-ene, tricyclo[3.2.1.02,7]oct-3-ene, and tricyclo[5.3.1.03,8]undec-9-ene derivatives through purely pericyclic, three-step homodomino processes with diverse bis-dienophiles; whereas the reaction with myrcene (21) was characterized by a complete sitoselectivity affording compound 25, treatment of 1 with (R)-(-)-β-citronellene (26a) gave a 3:1 mixture of the homochiral diastereomers 30a and 31a. Some limits of this methodology, mainly arising from competitive side reactions upon the key cyclohexa-1,3-diene intermediates, are emphasized. The structures of the new compounds were established on the basis of spectral data.
- Giomi, Donatella,Nesi, Rodolfo,Turchi, Stefania,Mura, Elena
-
-
Read Online
- Hetero Diels-Alder reactions of 4,5-dicyanopyridazine with alkenes
-
The behaviour of the title compound 1 with some linear and cyclic olefins has been investigated. Except for the reaction with diphenylcyclopropenone 22, affording 24 and 26 through cyclization processes of the primary Michael adduct 23, a remarkable reactivity as azadiene was observed. The structures of the resulting dicyanocyclohexa-1,3-dienes, aromatic phthalonitriles, and polycyclic bis-adducts were established on the basis of spectral data.
- Turchi, Stefania,Giomi, Donatella,Capaccioli, Caterina,Nesi, Rodolfo
-
-
Read Online
- Switchable activity of a Ru catalyst bearing an annulated mesoionic carbene ligand for oxidation of primary amines
-
The catalytic activity of a Ru complex 1, bearing a fused π-conjugated imidazo[1,2–a][1,8]naphthyridine-based mesoionic carbene (MIC) ligand, is examined for the oxidation of primary amines. Complex 1 affords nitrile or imine depending on the nature of th
- Bera, Jitendra K.,Din Reshi, Noor U,Pal, Nilay Kumar,Pal, Saikat,Pal, Sourav,Yadav, Suman
-
-
- Chemical Modifications Induced by Phthalic Anhydride, a Respiratory Sensitizer, in Reconstructed Human Epidermis: A Combined HRMAS NMR and LC-MS/MS Proteomic Approach
-
Chemical skin and respiratory allergies are becoming a major health problem. To date our knowledge on the process of protein haptenation is still limited and mainly derived from studies performed in solution using model nucleophiles. In order to better understand chemical interactions between chemical allergens and the skin, we have investigated the reactivity of phthalic anhydride 1 (PA), a chemical respiratory sensitizer, toward reconstructed human epidermis (RHE). This study was performed using a new approach combining HRMAS NMR to investigate the in situ chemical reactivity and LC-MS/MS to identify modified epidermal proteins. In RHE, the reaction of PA appeared to be quite fast and the major product formed was phthalic acid. Two amide type adducts on lysine residues were observed and after 8h of incubation, we also observed the formation of an imide type cyclized adducts with lysine. In parallel, RHE samples topically exposed to phthalic anhydride (13C)-1 were analyzed using the shotgun proteomics method. Thus, 948 different proteins were extracted and identified, 135 of which being modified by PA, i.e., 14.2% of the extracted proteome. A total of 211 amino acids were modified by PA and validated by fragmentation spectra. We thus identified 154 modified lysines, 22 modified histidines, 30 modified tyrosines, and 5 modified arginines. The rate of modified residues, as a proportion of the total number of modifiable nucleophilic residues in RHE, was rather low (1%). At the protein level, modified proteins were mainly type I and type II keratins and other proteins which are abundant in the epidermis such as protein S100A, Caspase 14, annexin A2, serpin B3, fatty-acid binding protein 5, histone H2, H3, H4, etc. However, the most modified protein, mainly on histidine residues, was filaggrin, a protein that is of low abundance (0.0266 mol %) and rich in histidine.
- Khong, Minh-Thuong,Berl, Valérie,Kuhn, Lauriane,Hammann, Philippe,Lepoittevin, Jean-Pierre
-
p. 2087 - 2099
(2021/08/30)
-
- An overview on the progress and development on the palladium catalyzed direct cyanation
-
Generation of the positive CN ion and the corresponding direct cyanation are both extremely important for cyanation of aromatic compounds. Hereby, we would like to report the simultaneous use of the new Pd nano-catalyst as well as the three types of the N-arylsulfonyl cyanamides (A, B and C) as potent reagents for the in situ generation of the positive CN ion for the direct cyanation of phenylboronic acids in acetonitrile at reflux conditions.
- Heydari, Somayyeh,Habibi, Davood,Reza Faraji, Ali,keypour, Hassan,Mahmoudabadi, Masoumeh
-
-
- Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
-
Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
- Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
-
-
- A Versatile VMPO Catalyst Prepared In Situ for Oxidative Ammonolysis of Isomeric Picolines and Xylenes
-
Abstract: The V2O5–MoO3–P2O5 (VMPO) catalyst has been prepared in situ by thermal decomposition of vanado-molybdophosphoric acid (PMoV) on TiO2 support at 475°C. The TiO2 supported VMPO catalysts are characterized by FT–IR, XRD, BET surface area, NH3–TPD, and H2–TPR. Morphology of the catalyst has been studied by TEM. The accumulated data indicate decomposition of PMoV and presence of phosphate and pyrophosphate phases of molybdenum and vanadium after calcination. TPD and TPR studies exhibit the moderate acidity and presence of V4+ in the material, respectively. The VMPO catalyst has been used for ammoxidation of six different compounds including three isomeric picolines and three isomeric xylenes to the corresponding nitriles with the yield of 90–96%.
- Dutta, P.,Pathak, D. D.,Senapati, Rabinarayan
-
p. 292 - 298
(2020/04/17)
-
- Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction
-
The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.
- Shah, Sk. Sheriff,Shee, Maniklal,Singh, N. D. Pradeep
-
supporting information
p. 4240 - 4243
(2020/04/22)
-
- Organic molecular material based on benzene ring unit and having long-afterglow effect and preparation method thereof
-
The invention discloses an organic molecular material based on benzene ring unit and having long-afterglow effect and a preparation method thereof. The structural formula of the organic material is represented as the specification, wherein Y1 to Y4 are respectively one or two of hydrogen atom and cyano group. By introducing the cyano groups in different number to different sites as electron withdrawing groups, the material has high synthetic efficiency and small molecule. When an excitation source is turned off, the material holds durable luminescence for a couple of seconds and has high fluorescent quantum efficiency. The material has an extensive potential application value in the fields such as anti-counterfeiting, bio-imaging, optic-electronic materials and the like.
- -
-
Paragraph 0053-0057
(2020/04/17)
-
- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
-
A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
-
supporting information
p. 1484 - 1488
(2019/07/15)
-
- Synthesis, characterization and catalytic performance of Pd(II) complex immobilized on Fe3O4@SiO2 nanoparticles for the ligand-free cyanation of aryl halides using K4Fe(CN)6
-
This work shows the preparation of a novel magnetic catalyst via immobilization of Pd(II)-N-benzyl-N-(4-bromophenyl)-5-amino-1H-tetrazole complex on the Fe3O4@SiO2 nanoparticles (NPs). The application of Fe3O4@SiO2 NPs supported Pd(II)-N-benzyl-N-(4-bromophenyl)-5-amino-1H-tetrazole complex [Fe3O4@SiO2-BAT-Pd(II)] nanocatalyst is described for the cyanation of aryl iodides and bromides to the corresponding aryl nitriles using potassium hexacyanoferrate(II) [K4Fe(CN)6] as a non-toxic and economic cyanating agent under ligand- and additive-free conditions. Some aryl nitriles were efficiently synthesized from the corresponding aryl bromides and iodides in the presence of Fe3O4@SiO2-BAT-Pd(II) nanocomplex. The core-shell nanocomplex demonstrated the superior catalytic performance for the synthesis of synthetically valuable aryl nitriles within good to excellent yields. This process eliminates the need to handle highly toxic metal cyanides, and it can be easily recovered and reused for six consecutive runs with no decreasing of its catalytic capability. Highlights: Preparation of Pd(II) complex immobilized on Fe3O4@SiO2 nanoparticles [Fe3O4@SiO2-BAT-Pd(II) nanocomplex]. Characterization of Fe3O4@SiO2-BAT-Pd(II) nanocomplex using XRD, FT-IR, EDS, VSM, TEM and FESEM analyses. Catalytic cyanation of the various aryl halides with K4Fe(CN)6 under ligand-free conditions. The nanocomplex can be recovered and isolated six times with no significant loss of its catalytic ability.
- Nasrollahzadeh, Mahmoud,Maryami, Mahboobe,Sajjadi, Mohaddeseh,Mehdipour, Ebrahim
-
-
- Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
-
A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
- Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
-
supporting information
p. 1434 - 1436
(2019/05/01)
-
- Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality
-
A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant-free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H2.
- Dutta, Indranil,Yadav, Sudhir,Sarbajna, Abir,De, Subhabrata,H?lscher, Markus,Leitner, Walter,Bera, Jitendra K.
-
supporting information
p. 8662 - 8666
(2018/07/09)
-
- A method for producing methyl benzoic acid, methyl benzonitrile and phthalonitrile method (by machine translation)
-
The invention discloses a method for producing methyl benzoic acid, methyl benzonitrile and phthalonitrile method, including: (1) to the oxidation reactor is injected continuously xylene, catalyst and an oxygen-containing gas to the reaction, oxidation reaction solution obtained; (2) the oxidation reaction solution into the initial steaming tower to separate rectification, when methyl methanol content in the [...] 0.01 - 0.15 wt % stop rectification, a low boiling point component and [...]; (3) will be [...] enter the rectifying tower for rectification, when the rectifying tower in [...] methyl benzoic acid content of 30 - 90 wt % stop rectification, to obtain the methyl benzoic acid products and rectifying tower [...]; (4) the spiral [...] mixed with ammonia, nitrile reaction solution obtained; (5) the nitrile reaction liquid to separate rectification, to respectively obtain the methyl benzonitrile and phthalonitrile product. The invention has simple process, equipment investment, environmental protection, integrated and good economic benefits. (by machine translation)
- -
-
Paragraph 0172-0188
(2018/12/13)
-
- NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
-
Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
- Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
-
p. 885 - 889
(2018/12/10)
-
- A Porous Organic Poly(triphenylimidazole) Decorated with Palladium Nanoparticles for the Cyanation of Aryl Iodides
-
A new porous organic poly(triphenylimidazole), PTPI-Me, was prepared through a Yamamoto self-coupling reaction of 2,4,5-tris-(4-bromophenyl)-1-methyl-1H-imidazole (TPI-Me) in the presence of bis(1,5-cyclooctadiene)nickel(0). The polymer was subsequently decorated with Pd nanoparticles (NPs) to afford a heterogeneous cyanation catalyst, Pd@PTPI-Me. Pd NPs with an average diameter of 2.7 nm were grown within the PTPI-Me framework, owing to the coordination of the imidazole rings to the Pd species. The resultant Pd@PTPI-Me catalyst, with a Pd loading of 0.13 mmol g?1, exhibited superior catalytic activity for the cyanation of aryl iodides. More importantly, the heterogeneous catalyst was also readily recycled and displayed negligible deactivation after five cycles.
- Yu, Haiwen,Xu, Siqi,Liu, Yijiang,Chen, Hongbiao,Li, Huaming
-
p. 2708 - 2713
(2018/09/06)
-
- Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues
-
The use of Pd(DPEPhos)Cl2 (P26) as a catalyst for the formation of benzonitriles and their heterocyclic analogues provides excellent complementarity to existing catalysts, allowing highly electron-deficient heterocyclic aryl halides to be effic
- Richardson, Jeffery,Mutton, Simon P.
-
p. 4922 - 4931
(2018/05/22)
-
- Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
-
Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
- Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
-
supporting information
p. 67 - 70
(2017/11/27)
-
- Preparation method of aromatic nitrile compound or heteroaromatic nitrile compound
-
The invention discloses a preparation method of an aromatic nitrile compound or a heteroaromatic nitrile compound. The preparation method comprises: under the protection of an inert gas, in a solvent,under the actions of a nickel catalyst, a ligand, metal zinc and an additive, carrying out a reaction on a cyanation reagent and halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon. According to the present invention, by using the inexpensive and easily-available nickel catalyst and the ligand, the halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon,especially the chlorinated aromatic hydrocarbon or chlorinated heteroaromatic hydrocarbon with characteristics of low price, easy obtaining and low reaction activity can mildly and efficiently react with the cyanation reagent with low toxicity to prepare the aromatic nitrile compound or heteroaromatic nitrile compound; and the preparation method has advantages of simple operation, mildness, high efficiency and the like, and further has characteristics of good functional group compatibility, good universality of substrate and the like.
- -
-
Paragraph 0043; 0045; 0142-0144
(2018/11/03)
-
- Catalyst-free, efficient and one pot protocol for synthesis of nitriles from aldehydes using glycerol as green solvent
-
We described herein the novel, efficient and one-pot catalyst free protocol for the synthesis of nitriles from aldehydes by using hydroxyl amine hydrochlorides in glycerol as a green solvent. This protocol was efficiently used for transformation of aromatic aldehydes bearing electron-withdrawing and electron-donating groups into a aryl nitriles in good to excellent yields. The methodology offers a very simple, efficient and environmentally benign procedure.
- Ingale, Ajit P.,Patil, Shripad M.,Shinde, Sandeep V.
-
p. 4845 - 4848
(2017/11/30)
-
- General and Mild Nickel-Catalyzed Cyanation of Aryl/Heteroaryl Chlorides with Zn(CN)2: Key Roles of DMAP
-
A new and general nickel-catalyzed cyanation of hetero(aryl) chlorides using less toxic Zn(CN)2 as the cyanide source has been developed. The reaction relies on the use of inexpensive NiCl2·6H2O/dppf/Zn as the catalytic system and DMAP as the additive, allowing the cyanation to occur under mild reaction conditions (50-80 °C) with wide functional group tolerance. DMAP was found to be crucial for successful transformation, and the reaction likely proceeds via a Ni(0)/Ni(II) catalysis based on mechanistic studies. The method was also successfully extended to aryl bromides and aryl iodides.
- Zhang, Xingjie,Xia, Aiyou,Chen, Haoyi,Liu, Yuanhong
-
supporting information
p. 2118 - 2121
(2017/04/27)
-
- A hydrophilic inorganic framework based on a sandwich polyoxometalate: Unusual chemoselectivity for aldehydes/ketones with in situ generated hydroxylamine
-
A hydrophilic inorganic porous catalyst was prepared via the hydrothermal method. The combination of [WZn3(H2O)2(ZnW9O34)2]12- and Co(ii) provides a synergistical catalytic way to promote oximation of aldehyde/ketone with in situ generated hydroxylamine that initially produces an oxime, which further either dehydrates into a nitrile or undergoes a Beckmann rearrangement to form an amide.
- Xing, Songzhu,Han, Qiuxia,Shi, Zhuolin,Wang, Shugai,Yang, Peipei,Wu, Qiang,Li, Mingxue
-
supporting information
p. 11537 - 11541
(2017/09/18)
-
- Pd/CuO nanoparticles as a highly effective catalyst for the cyanation of aryl halides under ligand-free conditions
-
Copper oxide supported palladium nanoparticles have been used as a separable catalyst for the cyanation of a range of aryl iodides and bromides under ligand-free conditions. The effect of solvent, base, and catalyst loading was investigated. The catalyst can easily be recovered and reused several times without significant loss of catalytic activity.
- Nasrollahzadeh, Mahmoud
-
p. 337 - 339
(2016/01/12)
-
- Visible light catalysis synthesis method of aryl cyanide
-
The invention discloses a visible light catalysis synthesis method of aryl cyanide. The method comprises the following steps: putting aryl halide, potassium ferrocyanide and alkali in an organic solvent; in the condition of magnetic stirring, starting a visible light source with power of 100-500W; irradiating with light intensity of 0.2-0.8W/cm until the reaction is over while controlling the reaction temperature at 25-85 DEG C; and carrying out a catalytic reaction for 1-12h by using a nano precious metal supported photocatalyst to synthesize the aryl cyanide. The photocatalysis cyaniding process can be shown by a general formula (I), wherein the X group is Br or I; and the R group is selected from electron attracting groups such as nitryl, acetyl and carboxyl and electron donating groups such as methoxy and methyl. In the invention, nontoxic green potassium ferrocyanide is used as a cyanogen source for synthesizing aryl cyanide, the highly toxic cyanides widely used in original methods are replaced, and thus the problem of environmental pollution in the aryl cyanide synthesis is reduced. The photocatalysis cyaniding reaction has the advantages of mild reaction conditions, stability and high efficiency, simplicity in operation, environmental friendliness, high product conversion rate and good selectivity.
- -
-
Paragraph 0052; 0053
(2017/02/28)
-
- Pd Catalysis in Cyanide-Free Synthesis of Nitriles from Haloarenes via Isoxazolines
-
A method to obtain aryl nitriles from the corresponding halides by Pd catalysis, in the absence of any cyanide source, is reported. The reaction of an aryl halide, ethyl nitroacetate, and an olefin readily delivers an aromatic nitrile. A variety of aryl iodides/bromides have been converted into the corresponding cyanoarenes in fair to excellent yields. The reaction likely involves the following steps: (a) Pd-catalyzed α-arylation of ethyl nitroacetate; (b) nitrile oxide formation; (c) [3 + 2]-cycloaddition with an olefin to provide an isoxazoline; (d) isoxazoline cleavage to benzonitrile formation.
- Maestri, Giovanni,Ca?eque, Tatiana,Della Ca, Nicola,Derat, Etienne,Catellani, Marta,Chiusoli, Gian Paolo,Malacria, Max
-
supporting information
p. 6108 - 6111
(2016/12/09)
-
- SYNTHESIS AND POLYMERIZATION OF OLIGOMERIC ALIPHATIC-AROMATIC BASED PHTHALONITRILES
-
A phthalonitrile compound having the formula below. The value n is a positive integer. Each R has a hydrocarbon chain optionally having —O— or —SiR′2—O—. Each R′ is an aliphatic group. Each Ar is an aromatic group with the proviso that Ar contains at least two aromatic rings when n is 1 and R is an alkylene group. A method of: reacting an excess of a dihydroxyaromatic compound with a dihalocompound to form an oligomer; and reacting the oligomer with 4-nitrophthalonitrile to form the phthalonitrile compound, where Ar is an aromatic group.
- -
-
-
- Aryl Nitriles from Alkynes Using tert -Butyl Nitrite: Metal-Free Approach to C≡C Bond Cleavage
-
Alkyne C≡C bond breaking, outside of alkyne metathesis, remains an underdeveloped area in reaction discovery. Recently, nitrogenation has been reported to allow nitrile formation from alkynes. A new protocol for the metal-free C≡C bond cleavage of terminal alkynes to produce nitriles is reported. This method provides an opportunity to synthesize a vast range of nitriles containing aryl, heteroaryl, and natural product derivatives (38 examples). In addition, the potential of tBuONO to act as a powerful nitrogenating agent for terminal aryl alkynes is demonstrated. (Figure Presented).
- Dutta, Uttam,Lupton, David W.,Maiti, Debabrata
-
supporting information
p. 860 - 863
(2016/03/01)
-
- Synthesis and catalytic activity of carbon supported copper nanoparticles for the synthesis of aryl nitriles and 1,2,3-triazoles
-
Various substituted aryl nitrile and 1,2,3-triazole derivatives were prepared by using carbon supported copper nanoparticles (C/Cu NPs) as a heterogeneous catalyst under ligand-free conditions, which provided good to excellent yields. The nanocatalyst can be recycled and reused several times without significant loss of catalytic activity.
- Nasrollahzadeh, Mahmoud,Jaleh, Babak,Fakhri, Parisa,Zahraei, Ali,Ghadery, Esmaeil
-
p. 2785 - 2793
(2015/02/02)
-
- Palladium/N-Heterocyclic carbene catalyzed mono- and double-cyanation of aryl halides using potassium ferrocyanide trihydrate under aerobic conditions
-
Abstract A practical palladium/N-heterocyclic carbene catalyzed procedure for the mono- and double-cyanation of aryl halides is described using inexpensive, easy-to-handle and nontoxic potassium ferrocyanide trihydrate {K4[Fe(CN)6]·3H2O} as the cyanating agent. The reaction does not require an anhydrous solvent, or the exclusion of air or moisture. A variety of electron-rich and electron-deficient aryl halides are efficiently converted into their corresponding nitriles and dicarbonitriles.
- Xu, Zhicheng,Xiao, Yunqing,Ding, Hong,Cao, Changsheng,Li, Haitao,Pang, Guangsheng,Shi, Yanhui
-
p. 1560 - 1566
(2015/06/02)
-
- Activity enhancement in cyanation of aryl halides through confinement of ionic liquid in the nanospaces of SBA-15 -supported Pd complex
-
A novel and practical ionic-liquid mediated route for the synthesis of various aromatic nitriles has been developed via the cyanation of aryl halides with K4[Fe(CN)6] as a low cost, non-toxic and easily handled cyanating reagent in the presence of SBA-15 functionalized palladium complex partially confined with ionic liquids (IL@SBA-15-Pd) as the catalyst. Among the various ionic liquids tested in the cyanation reaction, 1-butyl-3-methylimidazolium hexafluorophosphate was found to provide the best medium for Pd-catalyzed cyanation of aryl halides. A variety of electron-rich and electron-poor aryl iodides and bromides gave the corresponding benzonitrile derivatives in good yield. Moreover, the catalyst was reused in four consecutive cycles with consistent catalytic activity. It was found that the presence of ionic liquid in the mesochannels of the mesoporous support not only provides a means of stabilizing Pd nanoparticles during the reaction but also the salient phase transfer feature of the imidazolium moieties may also serve as handles for faster penetration of Fe(CN)63- into the system pores to achieve highly concentrated reaction sites in close proximity to the catalytic (Pd NPs) centers, which resulted in an enhancement of the catalyst activity performance. This journal is
- Karimi, Babak,Zamani, Asghar,Mansouri, Fariborz
-
p. 57639 - 57645
(2015/01/09)
-
- Copper nanoparticles from copper aluminum hydrotalcite: An efficient catalyst for acceptor- and oxidant-free dehydrogenation of amines and alcohols
-
An efficient and simple process for the preparation of stable nanocopper(0) on alumina [Cu(0)/Al2O3] from the inorganic composite precursor copper aluminum hydrotalcite (Cu-AlHT) by a chemical reduction method is described. Cu(0)/ Al2O3 was employed as an efficient catalyst in the acceptor- and oxidant-free dehydrogenation of various amines and alcohols to their corresponding dehydrogenated products in good to excellent yields. The stability of Cu(0)/Al2O3 was assessed by studying its recoverability and reusability in the dehydrogenation of amines and alcohols for up to five cycles.
- Damodara, Dandu,Arundhathi, Racha,Likhar, Pravin R.
-
supporting information
p. 189 - 198
(2014/03/21)
-
- Ultrasounds in melted poly(ethylene glycol) promote copper-catalyzed cyanation of aryl halides with K4[Fe(CN)6]
-
Melted poly(ethylene glycols) (PEGs) were used for the first time as solvent for the sonochemically promoted cyanation of aryl halides employing inexpensive and safe K4[Fe(CN)6] and a relatively low amount of Cu-based catalyst. The Mw (weight-average polymer molecular weight) of PEG proved to notably influence the substrate conversion, which is indicative of a strong dependence of the sonication efficacy on solvent properties. Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) contributed to the characterization of the polymer and the elucidation of the catalytic system. Off the PEG: Melted poly(ethylene glycol)s (PEG)s were used for the first time as solvent for the sonochemical cyanation of aryl halides using K 4[Fe(CN)6] and a relatively low amount of Cu catalyst (5 %). The weight-average molecular weight of PEG was proven to exert a notable influence on conversion, and CuI proved to be the most efficient catalyst, affording good results within short reaction times with the use of aryl iodides and activated aryl bromides as substrates.
- Giachi, Guido,Frediani, Marco,Oberhauser, Werner,Lamaty, Frederic,Martinez, Jean,Colacino, Evelina
-
p. 919 - 924
(2014/03/21)
-
- Silica-functionalized N-propylpiperazine for immobilization of palladium nanoparticles as efficient heterogeneous catalyst for cyanation reactions
-
An efficient heterogeneous Pd catalytic system has been developed, based on immobilization of Pd nanoparticles (PNPs) on a silica-bonded N-propylpiperazine (SBNPP) substrate. The SBNPP substrate effectively stabilizes the PNPs and improves their stability against aggregation. The catalytic activity of this catalyst was investigated in the cyanation of aryl halides with K 4[Fe(CN)6] as the cyanide source. The catalyst could be recycled several times without appreciable loss of catalytic activity.
- Niknam, Khodabakhsh,Deris, Abdollah,Panahi, Farhad
-
p. 718 - 722
(2013/08/25)
-
- Palladium catalyzed cyanation of o-dichloroarenes with potassium hexacyanoferrate(ii)
-
Cyanation of o-dichloroarenes with potassium hexacyanoferrate(ii) catalyzed by Pd(OAc)2/PPh3 system gave the corresponding phthalodinitriles in moderate yields. The method of competitive reactions revealed that activation rate of chl
- Savicheva,Boyarskiy
-
p. 980 - 983
(2013/07/25)
-
- A chemoselective, one-pot transformation of aldehydes to nitriles
-
This paper describes a procedure for direct conversion of aldehydes to nitriles using O-(diphenylphosphinyl)hydroxylamine (DPPH). Aldehydes are smoothly transformed to their corresponding nitriles by heating with DPPH in toluene. The reaction can be accomplished in the presence of alcohol, ketone, ester, or amine functionality.
- Laulhe, Sebastien,Gori, Sadakatali S.,Nantz, Michael H.
-
p. 9334 - 9337,4
(2012/12/12)
-
- A chemoselective, one-pot transformation of aldehydes to nitriles
-
This paper describes a procedure for direct conversion of aldehydes to nitriles using O-(diphenylphosphinyl)hydroxylamine (DPPH). Aldehydes are smoothly transformed to their corresponding nitriles by heating with DPPH in toluene. The reaction can be accomplished in the presence of alcohol, ketone, ester, or amine functionality.
- Laulhé, Sébastien,Gori, Sadakatali S.,Nantz, Michael H.
-
p. 9334 - 9337
(2013/01/15)
-
- High temperature vapor phase reactions of nitrogen trifluoride with benzylic substrates
-
At temperatures around 400°C, nitrogen trifluoride (NF3) readily reacts with benzylic substrates. Products vary with the substrate, but are all the result of difluoroamination at the benzylic position. Toluene and ethylbenzene produce benzonitrile. Cumene produces α-methylstyrene. Diphenylmethane produces benzanilide. Little or no direct fluorination or radical dimerization is observed.
- Belter, Randolph K.
-
experimental part
p. 318 - 322
(2011/06/26)
-
- AROMATIC ETHER AND ALKYNYL CONTAINING PHTHALONITRILES
-
Compounds having the formulas below. R is an aromatic-containing group. Each M is an alkali metal. Each m is a positive integer. The value of n is a positive integer. The value p is 0 or 1. If p is 0 then n is 1. A thermoset made by curing a composition containing the below phthalonitrile monomers. A method of reacting a diphenyl acetylene compound with an excess of an aromatic diol in the presence of an alkali metal carbonate to form the above oligomer. A method of reacting a phenoxyphthalonitrile with an acetylene compound to form the phthalonitrile monomer below.
- -
-
-
- A bio-inspired copper catalyst system for practical catalytic cyanation of aryl bromides
-
A general and environmentally improved protocol for the cyanation of aryl halides with the nontoxic cyanide source potassium hexacyanoferrate(II) {K 4[Fe(CN)6]} using copper catalysis and a ligand system based on 1-alkyl-1H-imidazoles is presented. The advantages of this system are a wide substrate range, high selectivity, easy handling, and inexpensive reagents.
- Schareina, Thomas,Zapf, Alexander,Cotte, Alain,Mueller, Nikolaus,Beller, Matthias
-
experimental part
p. 3351 - 3355
(2009/06/06)
-
- Synthesis of phthalonitriles using a palladium catalyst
-
An easy synthetic method to obtain phthalonitriles from o-dibromobenzenes under mild conditions in high yields using Zn(CN)2 and a catalytic amount of tris(dibenzylideneacetone)dipalladium and 1,1′- bis(diphenylphosphino)ferrocene is described. Georg Thieme Verlag Stuttgart.
- Iqbal, Zafar,Lyubimtsev, Alexey,Hanack, Michael
-
experimental part
p. 2287 - 2290
(2009/05/07)
-
- CAN-mediated oxidation of electron-deficient aryl and heteroaryl hydrazines and hydrazides
-
Aryl and heteroaryl hydrazines and hydrazides were successfully oxidised using CAN, deriving dehydrazinated products. The reaction pathway strongly depends on the nature of the substrate, resulting in the formation of hydrocarbons or alkoxy derivatives. When deuterated solvents such as methanol-d4 or acetonitrile-d3 were used, a regiospecific incorporation of deuterium was achieved. Georg Thieme Verlag Stuttgart.
- ?tefane, Bogdan,Polanc, Slovenko
-
scheme or table
p. 1279 - 1282
(2009/04/06)
-
- A state-of-the-art cyanation of aryl bromides: A novel and versatile copper catalyst system inspired by nature
-
A general protocol for the cyanation of aryl halides with the nontoxic cyanide source K4[Fe(CN)6] using copper catalysis and a ligand system based on 1-alkylimidazoles is presented. The advantages of this system are the high selectivity, a unique substrate range, easy handling, and inexpensive reagents.
- Schareina, Thomas,Zapf, Alexander,Maegerlein, Wolfgang,Mueller, Nikolaus,Beller, Matthias
-
p. 6249 - 6254
(2008/02/13)
-
- UV-visible spectral study on the stability of lead phthalocyanine complexes
-
UV-visible electronic spectral study has been done on lead phthalocyanine (PbPc), lead tetranitro phthalocyanine (PbTNP) and lead tetraamino phthalocyanine (PbTAP) in dimethyl sulphoxide (DMSO) and H2SO4 media. Metal free phthalocyanine (H2Pc) is insoluble in DMSO and soluble in conc. H2SO4. The study has been extended to H2Pc to compare the stability of phthalocyanine structure with the PbPc complexes in H2SO4 medium. PbPc complexes are stable in DMSO, and all the complexes are more stable in 36 N H2SO4 than in 30 N and 28 N H2SO4 media. Further, complete demetallation and degradation of the phthalocyanine structure have been observed for all the PbPc complexes in 36 N H2SO4 medium within a week's time. The stability of these complexes is compared with H2Pc in H2SO4 medium. The decomposition reactions in H2SO4 media for H2Pc, PbPc, PbTNP and PbTAP are followed spectrophotometrically and rate constants were calculated. The decomposition reactions were found to follow the first-order kinetics with respect to the concentration of their respective phthalocyanine derivatives.
- Mohan kumar,Achar
-
p. 2282 - 2288
(2008/10/09)
-
- Rhodococcus nitrile hydratase
-
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.
- -
-
-
- Reductive elimination of C-CN compounds from nickel complexes as a reverse reaction for oxidative addition of benzonitriles to nickel
-
Treatment of (bpy)Ni(CN)(C6H4CN-o or -m) with acrylonitrile led to reductive elimination of CNC6H4CN from the complex. The reductive elimination proceeded much faster for the C6H4CN-m complex.
- Yamamoto, Takakazu,Yamaguchi, Isao,Abla, Mahmut
-
p. 179 - 182
(2015/03/05)
-
- Reductive elimination of C-CN compounds from nickel complexes as a reverse reaction for oxidative addition of benzonitriles to nickel
-
Treatment of (bpy)Ni(CN)(C6H4CN-o or -m) with acrylonitrile led to reductive elimination of CN-C6H4CN from the complex. The reductive elimination proceeded much faster for the C6H4CN-m complex.
- Yamamoto, Takakazu,Yamaguchi, Isao,Abla, Mahmut
-
p. 179 - 182
(2007/10/03)
-
- Beta-cyclodextrin dimers and phthalocyanines and uses thereof
-
The invention provides β-cyclodextrin dimers and phthalocyanines which can be used in photodynamic therapy of cancer.
- -
-
-
- Thermodynamics of the donor-acceptor interaction of zinc(II)tetraphenylporphyrin with mono- and dinitriles
-
Calorimetric titration was used for the first time to measure the thermodynamic characteristics of complexation of zinc(II) tetraphenylporphyrin with mono- and dinitriles. The effect of the electronic structure and the electron density distribution in the molecular ligands on the thermodynamic characteristics was examined. In passing from the benzene to the carbon tetrachloride solvent, both the exothermicity of the reactions under study and the stability of the complexes formed increase.
- Lebedeva,Mikhailovskii,V'yugin,Davydova
-
p. 1028 - 1030
(2007/10/03)
-
- New applications of Ph3P=N-Li in organic synthesis and heteroatom chemistry
-
The lithium triphenylaminophosphonium azayldiide 1 proved again to be a very good tool in organic synthesis, allowing further synthesis of various compounds such as vinyl nitriles, aromatic or heteroaromatic nitriles, and mono-, bis-, and trisphosphinimines.
- Taillefer, Marc,Rahier, Nicolas,Minta, Ewelina,Cristau, Henri-Jean
-
p. 1847 - 1850
(2007/10/03)
-
- Electrochemical reduction of 1,4-disubstituted phthalazines
-
Electrochemical reduction in dimethylformamide of unsymmetrical 1-Cl-4-X-phthalazines and symmetrical 1,4-X2-phthalazines (X = Cl, PhO, MeO, EtO, i-PrO) was studied by voltammetry and electrolysis-ESR. The electron trasfer on 1,4-dichlorophthalazine and unsymmetrical 1-Cl-4-X-phthalazines induces anionoid elimination of Cl and X, pyridazine ring cleavage, and phthalonitrile formation. In this previously unknown process the transfer of two electrons induces cleavage of three σ bonds and formation of two new π bonds. The reduction of 1,4-dialkoxy(diaryloxy)phthalazines involves formation of stable radical anions which undergo no heteroring cleavage. Possible mechanisms of the processes studied were discussed. It was assumed that the same mechanism with pyridazine ring cleavage may be realized with other phthalazine derivatives and heteroannelated pyridazines containing readily leaving nucleofuge groups α to nitrogens.
- Yanilkin,Buzykin,Morozov,Nastapova,Maksimyuk,Eliseenkova
-
p. 1636 - 1646
(2007/10/03)
-
- A new palladium catalyst system for the cyanation of aryl chlorides
-
The influence of reaction conditions and additives on the palladium-catalyzed cyanation of aryl chlorides with potassium cyanide has been investigated. Successful cyanation of aryl chlorides is observed in the presence of palladium catalysts using potassium cyanide. It is shown that the combination of a 1,5-bis(diphenylphosphino)pentane ligand and the addition of N,N,N′,N′-tetramethylethylenediamine (TMEDA) as a co-catalyst are the key factors in obtaining the corresponding aryl nitriles with improved catalyst productivities and selectivities.
- Sundermeier, Mark,Zapf, Alexander,Beller, Matthias,Sans, Jürgen
-
p. 6707 - 6710
(2007/10/03)
-
- Reactivity of alkylbenzenes in oxidative ammonolysis on vanadium-zirconium oxide catalyst
-
The reactivity of alkylbenzenes in oxidative ammonolysis on the vanadium-zirconium oxide catalyst increases in the order toluene, m-xylene, o-xylene, p-xylene, and ethylbenzene. The rate constants of transformation of alkyl substituents into the CN group correlate with the enthalpies of their deprotonation in the gas phase.
- Vorob'ev,Mikhailovskaya,Gabdullina,Sembaev
-
p. 1248 - 1250
(2007/10/03)
-