- From 1,3-dicyanobenzene to 3-cyanobenzamide - Its molecular structure in the gas-phase and in the crystal
-
The crystals of 3-cyanobenzamide have been obtained in the reaction of MgPcH2O with 1,3-dicyanobenzene. 3-Cyanobenzamide crystallises in the P21/c space group of the monoclinic system with four molecules per unit cell. In the crystal, the 3-cyanobenzamide molecule is non-planar, the amide group is rotated by 21.8(1)° around the Car-Csp2 bond in relation to the phenyl ring. Full optimised molecular orbital calculations performed on the isolated 3-cyanobenzamide molecule have shown a similar conformation (the rotation angle equals to 22.46°). Two pairs of symmetric equivalent N-H?O and N-H?N hydrogen bonds with two neighbouring form pseudo one-dimensional chains interconnect each 3-cyanobenzamide molecule in the crystal. The chains of 3-cyanobenzamide molecules form a stacking structure with π?π interactions between the aromatic phenyl rings within the stacks. The molecular orbital calculations and conformational analysis have shown two equivalent pairs minimum of energy on the potential energy surface (PES) - one global, other local. During rotation of the amide group from 0 to 360° around the Car-Csp2 bond four rotation barriers are observed. The highest rotation barrier energy of 48.84 kJ mol-1 is compared to the hydrogen bond energy.
- Janczak, Jan,Kubiak, Ryszard
-
-
Read Online
- Mechanochemical synthesis of half-sandwich iridium/rhodium complexes with 8-hydroxyquinoline derivatives ligands
-
Mechanochemistry provides a rapid, efficient route to half-sandwich iridium and rhodium complexes from [MCp*(μ-Cl)Cl]2 (M = Ir, Rh) and 8-hydroxyquinoline-2-carbaldehyde without the need for Schlenk manipulation, inert gas protection, or dry solvents. Furthermore, post-synthetic modification of the half-sandwich metal complexes has been carried out via a mechanochemical Wittig reaction between half-sandwich metal complex and phosphorus ylide. All complexes were fully characterized by 1H and 13C NMR spectra, infrared spectroscopy, mass spectrometry, and single-crystal X-ray diffraction method. The half-sandwich rhodium complexes exhibited high catalytic activity towards the amide synthesis between aldehyde and hydroxylamine hydrochloride (NH2OH·HCl) with a broad functional group tolerance.
- Jia, Wei-Guo,Li, Xiao-Dong,Zhi, Xue-Ting,Zhong, Rui
-
-
- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
-
Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
-
supporting information
p. 3595 - 3599
(2021/06/06)
-
- One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
-
Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
- Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
-
supporting information
p. 7961 - 7964
(2019/10/11)
-
- Method for preparing derivatives of benzamide under microwave condition in aqueous phase
-
The invention discloses a method for preparing derivatives of benzamide under a microwave condition in an aqueous phase. A coupling reaction is carried out between substituted benzoic acid and amine under the microwave condition in the aqueous phase. The method for preparing the derivatives of benzamide is environmentally friendly, easy and convenient to operate, safe, low in cost and efficient. Compared with the prior art, the method can be applicable to a large number of functional groups, is high in yield, produces fewer by-products, and further is easy to operate, safe, low in cost and environmentally friendly. A formula is shown in the description.
- -
-
Paragraph 0018; 0103
(2019/03/28)
-
- Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature
-
Transition-metal-catalyzed nitrile hydration is an atom-economic method for the synthesis of various amides. This work demonstrates for the first time that the addition of non-redox metal ions like Sc3+ dramatically accelerate the hydration of various nitriles to amides at ambient temperature with the simple Pd(OAc)2 salt as catalyst, whereas the reactions with Pd(OAc)2 alone were very sluggish. The formation of a heterobimetallic PdII/ScIII species has been proposed as the key species for the hydration that demonstrates a bimetallic synergistic effect in this process.
- Zhang, Sicheng,Xu, Haosheng,Lou, Chenlin,Senan, Ahmed M.,Chen, Zhuqi,Yin, Guochuan
-
p. 1870 - 1875
(2017/04/21)
-
- Supported Gold Nanoparticles-Catalyzed Microwave-Assisted Hydration of Nitriles to Amides under Base-Free Conditions
-
Polystyrene-supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV-visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water-mediated reaction conditions. (Figure presented.).
- Kumar, Sandeep,Sharma, Saurabh,Das, Pralay
-
supporting information
p. 2889 - 2894
(2016/09/16)
-
- Homogeneous and stereoselective copper(II)-catalyzed monohydration of methylenemalononitriles to 2-cyanoacrylamides
-
A facile and efficient route for the homogeneous and highly stereoselective monohydration of substituted methylenemalononitriles to (E)-2-cyanoacrylamides catalyzed by copper(II) acetate monohydrate in acetic acid containing 2% water is described, and a mechanism is proposed. The protocol has proved to be suitable for the monohydration of dicyanobenzenes and 2-substituted malononitriles.
- Xin, Xiaoqing,Xiang, Dexuan,Yang, Jiming,Zhang, Qian,Zhou, Fenguo,Dong, Dewen
-
p. 11956 - 11961
(2014/01/06)
-
- Solid-supported ruthenium(0): An efficient heterogeneous catalyst for hydration of nitriles to amides under microwave irradiation
-
Solid-supported ruthenium(0) was synthesized by the reduction deposition method and used as a heterogeneous catalyst for the hydration of nitriles to amides under microwave irradiation. A wide range of aromatic, α,β-unsaturated and aliphatic nitriles were efficiently converted to their corresponding primary amides under milder conditions. The catalyst was found to be very stable under moisture and microwave irradiation, easily separable from the reaction mixture, to cause negligible metal contamination of the product and was recyclable up to ten times without significant loss of catalytic activity.
- Kumar, Sandeep,Das, Pralay
-
supporting information
p. 2987 - 2990
(2013/10/01)
-
- Transition metal-free sodium borohydride promoted controlled hydration of nitriles to amides
-
A transition metal-free process, promoted by sodium borohydride, has been developed for convenient and selective hydration of nitriles to corresponding amides. The present process converts the aromatic, aliphatic, and heteroaromatic nitriles with wide functional group tolerance. The regioselective hydration of one nitrile moiety in the presence of an other nitrile group makes high impact in the present protocol.
- Verma, Praveen Kumar,Kumar, Neeraj,Sharma, Upendra,Bala, Manju,Kumar, Vishal,Singh, Bikram
-
p. 2867 - 2875
(2013/09/02)
-
- A general and efficient heterogeneous gold-catalyzed hydration of nitriles in neat water under mild atmospheric conditions
-
Mild, efficient and general: Titania decorated with nanometer-sized gold particles acts as an efficient catalyst for the selective hydration of a wide range of chemically diverse nitriles into valuable amides in neutral water, under mild atmospheric conditions (see image). The process shows promise for a facile and direct one-pot synthesis of ?μ-caprolactam, an industrially important molecule, starting from 6-aminocapronitrile. Copyright
- Liu, Yong-Mei,He, Lin,Wang, Miao-Miao,Cao, Yong,He, He-Yong,Fan, Kang-Nian
-
scheme or table
p. 1392 - 1396
(2012/10/07)
-
- Chemistry by nanocatalysis: First example of a solid-supported RAPTA complex for organic reactions in aqueous medium
-
A ruthenium-arene-PTA (RAPTA) complex has been supported for the first time on an inorganic solid, that is, silica-coated ferrite nanoparticles. The resulting magnetic material proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentration, environmentally friendly water as a reaction medium, with no use at all of organic solvent during or after the reactions, and microwaves as an alternative energy source renders the synthetic processes reported herein "truly" green and sustainable. RAPTA's delight: A nano-RAPTA complex supported on silica-coated ferrite nanoparticles proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentrations, water as a reaction medium, and microwaves as an energy source renders these processes green and sustainable.
- García-Garrido, Sergio E.,Francos, Javier,Cadierno, Victorio,Basset, Jean-Marie,Polshettiwar, Vivek
-
experimental part
p. 104 - 111
(2012/01/06)
-
- Ligand-free nickel-catalyzed conversion of aldoximes into nitriles
-
Catalytic dehydration of aldoximes can be performed efficiently with NiCl2 in acetonitrile under neutral and mild conditions. Under these conditions, various functionalized aldoximes produce the corresponding nitriles in good to excellent yields. Georg Thieme Verlag Stuttgart. New York.
- Li, Yen-Ting,Liao, Bei-Sih,Chen, Hsin-Pei,Liu, Shiuh-Tzung
-
experimental part
p. 2639 - 2643
(2011/10/04)
-
- Pyrazole derivatives
-
This invention relates to pyrazole derivatives of formula (I) or pharmaceutically acceptable salts, solvates or derivatives thereof, and to processes for the preparation thereof, intermediates used in their preparation of, compositions containing them and the uses of such derivatives. The compounds of the present invention bind to the enzyme reverse transcriptase and are modulators, especially inhibitors thereof. As such, the compounds of the present invention are useful in the treatment of a variety of disorders including those in which the inhibition of reverse transcriptase is implicated. Disorders of interest include those caused by Human Immunodificiency Virus (HIV) and genetically related retroviruses, such as Acquired Immune Deficiency Syndrome (AIDS).
- -
-
-
- SUBSTITUTED THIAZOLE DERIVATIVES BEARING 3-PYRIDYL GROUPS, PROCESS FOR PREPARING THE SAME AND USE THEREOF
-
The present invention provides a pharmaceutical composition having a steroid C17,20-lyase inhibitory activity, which is useful as a prophylactic or therapeutic agent of prostatism, tumor such as breast cancer and the like, more particularly, a steroid C17,20-lyase inhibitor containing a compound represented by the formula: wherein A1 is an aromatic hydrocarbon group optionally having substituents or a heterocyclic group optionally having substituents, one of A2 and A3 is a hydrogen atom, a halogen atom, a C1-4 aliphatic hydrocarbon group optionally having substituents or an optionally esterified carboxyl group, the other of A2 and A3 is an aromatic hydrocarbon group optionally having substituents or a heterocyclic group optionally having substituents, and at least one of A1, A2 and A3 is a 3-pyridyl group optionally having substituents, or a salt thereof or a prodrug thereof.
- -
-
Page/Page column 53
(2008/06/13)
-
- Method of purifying isophthalonitrile
-
In a method for separating isophthalonitrile from a gas produced by causing m-xylene to react with ammonia and oxygen-containing gas in the presence of a catalyst, the gas is brought into contact with an organic solvent having a boiling point lower than that of isophthalonitrile; a liquid in which isophthalonitrile is trapped in a trapping step is distilled, to thereby recover isophthalonitrile and the organic solvent from the top of the column and separate at the bottom of the column impurities having boiling points higher than that of isophthalonitrile; and the organic solvent is recovered from the top of the rectification column and liquefied isophthalonitrile of high purity is recovered at the bottom of the column. Thus, loss of isophthalonitrile and plugging of a vacuum-evacuation system caused by isophthalonitrile migrating from a condensation system during distillation under reduced pressure can be prevented, and high-purity isophthalonitrile can be produced at high yield constantly for a long period of time.
- -
-
-
- Regioselective Hydrolysis of Aromatic Dinitriles Using a Whole Cell Catalyst
-
A series of aromatic dinitriles have been examined as substrates for an immobilised whole cell Rhodococcus sp. that catalyses the hydrolysis of nitriles to amides and/or carboxylic acids.The fluorinated aromatic dinitriles 48 and 49 were regioselectively hydrolysed to the corresponding cyano amides 48a and 49a whereas the non-fluorinated analogues 41-44 were converted to cyano acids but with poorer regioselectivity.
- Crosby, John,Moilliet, Jock,Parratt, Julian S.,Turner, Nicolas J.
-
p. 1679 - 1688
(2007/10/02)
-