- Reactivity of molybdenum-nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles
-
A molybdenum-nitride complex bearing a pyridine-based PNP-type pincer ligand derived from dinitrogen is reacted with various kinds of carbon-centered electrophiles to functionalize the nitride ligand in the molybdenum complex. Methylation with MeOTf and acylation with diphenylacetyl chloride of the nitride complex afford the corresponding imide complexes via a carbon-nitrogen bond formation. In the case of reactions with phenylisocyanate and diphenylketene, the PNP ligand works as a non-innocent ligand to form the corresponding ureate and acylimide complexes, respectively. These newly synthesized complexes are characterized by X-ray analysis. As a further transformation of the prepared imide complexes, hydrolysis of the molybdenum-acylimide complex proceeds to give the corresponding amide as an organonitrogen compound together with the corresponding molybdenum-oxo complex. This result indicates that the nitrogen molecule is converted into organic amide mediated by the molybdenum-nitride complex.
- Arashiba, Kazuya,Itabashi, Takayuki,Kuriyama, Shogo,Nishibayashi, Yoshiaki
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p. 1946 - 1954
(2022/02/11)
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- Bis-Rhodamines Bridged with a Diazoketone Linker: Synthesis, Structure, and Photolysis
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Two fluorophores bound with a short photoreactive bridge are fascinating structures and remained unexplored. To investigate the synthesis and photolysis of such dyes, we linked two rhodamine dyes via a diazoketone bridge (?COCN2?) attached to p
- Belov, Vladimir N.,Bossi, Mariano L.,Hell, Stefan W.,Shojaei, Heydar
-
-
- Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
-
The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.
- Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
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p. 7284 - 7296
(2021/05/29)
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- Catalytic C-C coupling of diazo compounds with arylboronic acids: Using surface modified sewage sludge as catalyst
-
A green, mild and efficient synthesis of diarylmethines using sewage sludge-derived carbonaceous materials (SW) by perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction shows a high level of functional tolerance and a broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift products were furnished through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone). The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the synthesis of the core structures of darifenacin (a clinical drug for overactive bladder syndrome, OAB) and diclofensine (a stimulant drug showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic potential of this method. This journal is
- Huang, Fei,Huang, He,Hughes, Timothy,Xie, Yuxing,Xu, Jun,Yu, Yang,Zhang, Zhipeng
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p. 4165 - 4173
(2020/07/14)
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- One-pot method for the synthesis of 1-aryl-2-aminoalkanol derivatives from the corresponding amides or nitriles
-
We have identified a novel one-pot method for the synthesis of β-amino alcohols, which is based on C-H bond hydroxylation at the benzylic α-carbon atom with a subsequent nitrile or amide functional group reduction. This cascade process uses molecular oxygen as an oxidant and sodium bis(2-methoxyethoxy)aluminum hydride as a reductant. The substrate scope was examined on 30 entries and, although the respective products were provided in moderate yields only, the above simple protocol may serve as a direct and powerful entry to the sterically congested 1,2-amino alcohols that are difficult to prepare by other routes. The plausible mechanistic rationale for the observed results is given and the reaction was applied to a synthesis of a potentially bioactive target. This journal is
- Bobal, Pavel,Otevrel, Jan,Svestka, David
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p. 25029 - 25045
(2020/07/14)
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- Direct synthesis of amides from nonactivated carboxylic acids using urea as nitrogen source and Mg(NO3)2or imidazole as catalysts
-
A new method for the direct synthesis of primary and secondary amides from carboxylic acids is described using Mg(NO3)2·6H2O or imidazole as a low-cost and readily available catalyst, and urea as a stable, and easy to manipulate nitrogen source. This methodology is particularly useful for the direct synthesis of primary and methyl amides avoiding the use of ammonia and methylamine gas which can be tedious to manipulate. Furthermore, the transformation does not require the employment of coupling or activating agents which are commonly required.
- Blacker, A. John,Chhatwal, A. Rosie,Lomax, Helen V.,Marcé, Patricia,Williams, Jonathan M. J.
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p. 5808 - 5818
(2020/06/21)
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- A continuous-flow synthesis of primary amides from hydrolysis of nitriles using hydrogen peroxide as oxidant
-
A continuous-flow synthesis of primary amides from hydrolysis of nitriles using hydrogen peroxide as oxidant has been developed. Using this procedure, a variety of nitriles could be smoothly transformed into the desired primary amides in good to excellent yields. The mild reaction conditions and the flowing reaction system greatly improved the safety and make the reaction easy to scale up.
- Zhan, Wei,Ji, Ling,Ge, Ze-mei,Wang, Xin,Li, Run-tao
-
p. 1527 - 1532
(2018/02/21)
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- Development and Utilization of a Palladium-Catalyzed Dehydration of Primary Amides to Form Nitriles
-
A palladium(II) catalyst, in the presence of Selectfluor, enables the efficient and chemoselective transformation of primary amides into nitriles. The amides can be attached to aromatic rings, heteroaromatic rings, or aliphatic side chains, and the reactions tolerate steric bulk and electronic modification. Dehydration of a peptaibol containing three glutamine groups afforded structure-activity relationships for each glutamine residue. Thus, this dehydration can act similarly to an alanine scan for glutamines via synthetic mutation.
- Al-Huniti, Mohammed H.,Rivera-Chávez, José,Colón, Katsuya L.,Stanley, Jarrod L.,Burdette, Joanna E.,Pearce, Cedric J.,Oberlies, Nicholas H.,Croatt, Mitchell P.
-
supporting information
p. 6046 - 6050
(2018/09/27)
-
- Hemilability-Driven Water Activation: A NiII Catalyst for Base-Free Hydration of Nitriles to Amides
-
The NiII complex 1 containing pyridyl- and hydroxy-functionalized N-heterocyclic carbenes (NHCs) is synthesized and its catalytic utility for the selective nitrile hydration to the corresponding amide under base-free conditions is evaluated. The title compound exploits a hemilabile pyridyl unit to interact with a catalytically relevant water molecule through hydrogen-bonding and promotes a nucleophilic water attack to the nitrile. A wide variety of nitriles is hydrated to the corresponding amides including the pharmaceutical drugs rufinamide, Rifater, and piracetam. Synthetically challenging α-hydroxyamides are accessed from cyanohydrins under neutral conditions. Related catalysts that lack the pyridyl unit (i.e., compounds 2 and 4) are not active whereas those containing both the pyridyl and the hydroxy or only the pyridyl pendant (i.e., compounds 1 and 3) show substantial activity. The linkage isomer 1′ where the hydroxy group is bound to the metal instead of the pyridyl group was isolated under different crystallization conditions insinuating a ligand hemilabile behavior. Additional pKa measurements reveal an accessible pyridyl unit under the catalytic conditions. Kinetic studies support a ligand-promoted nucleophilic water addition to a metal-bound nitrile group. This work reports a Ni-based catalyst that exhibits functional hemilability for hydration chemistry.
- Singh, Kuldeep,Sarbajna, Abir,Dutta, Indranil,Pandey, Pragati,Bera, Jitendra K.
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p. 7761 - 7771
(2017/06/06)
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- Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
-
A transition metal-free process, catalyzed by tetrabutylammonium hydroxide (TBAH), has been developed for the convenient and selective hydration of nitriles to the corresponding amides. The present process converts aromatic, aliphatic, and heteroaromatic nitriles with a wide variety of functional groups into amides. The regioselective hydration of one nitrile moiety in the presence of another nitrile group gives the present protocol high impact.
- Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
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p. 6365 - 6371
(2015/02/19)
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- An efficient synthesis of substituted isoxazolopyrroloisoquinolines via diastereoselective N-acyliminium ion cyclization
-
A simple and efficient strategy was developed for the synthesis of fused pyrrolo[2,1-a]isoquinoline ring systems. The 5- and 6-substituted isoxazolopyrroloisoquinolines were readily prepared via diastereoselective N-acyliminium ion cyclization of 5-(1-R(or 2-R)-substituted-2-phenylethyl)-6-hydroxytetrahydro-4H-pyrrolo[3,4-d]isoxazol-4-ones derived from the corresponding bicyclic dihydroisoxazoles.
- Ledovskaya, Maria S.,Molchanov, Alexander P.,Boitsov, Vitaly M.,Kostikov, Rafael R.,Stepakov, Alexander V.
-
supporting information
p. 1952 - 1958
(2015/04/14)
-
- Synthesis of α-Arylcarboxylic acid amides from silyl enol ether via migratory Amidation with 2-azido-1,3-dimethylimidazolinium hexafluorophosphate
-
α-Arylcarboxylic acid amides were synthesized by reacting silyl enol ethers of aryl ketones and 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP,1). Silyl enol ethers react with ADMP 1 to give N-(α-arylacyl) guanidines via the migration of aryl groups in enol ethers. The products were transformed to the corresponding α-aryl acetamides by treating with LiAlH4.
- Kitamura, Mitsuru,Murakami, Kento,Shiratake, Yuichiro,Okauchi, Tatsuo
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p. 691 - 693
(2013/07/26)
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- Selective hydration of nitriles to amides promoted by an Os-NHC catalyst: Formation and X-ray characterization of κ2-amidate intermediates
-
The complex [Os(η6-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO 3) reacts with benzonitrile and acetonitrile to afford the κ2-amidate derivatives [Os(η6-p-cymene) {κ2O,N-NHC(O)R}IPr]OTf (R = Ph (2), CH3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(η6-benzene)(OH)(CH3CN)IMe] + (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the κ2-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed.
- Buil, Maria L.,Cadierno, Victorio,Esteruelas, Miguel A.,Gimeno, Jose,Herrero, Juana,Izquierdo, Susana,Onate, Enrique
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p. 6861 - 6867
(2012/11/13)
-
- Electrochemical oxidation of amides of type Ph2CHCONHAr
-
Anodic oxidation of N-aryl-2,2-diphenylacetamides in acetonitrile undergoes three types of bond-cleavage, one between the benzylic carbon and the carbonyl group, the second between a carbonyl and 'N', and the third between the 'N' atom and aryl group. The selectivity of the cleavage and nature of emerged products is highly dependent on the nature of substituent attached to the aryl group. For example, electron-withdrawing groups direct the benzyl-carbonyl bond-breaking whereas electron-donating substituents favor the N-aryl bond cleavage. The type of products obtained involve benzophenone, 2,2-diphenylacetamide, N-(diphenylmethylene)acetamide, N-(diphenylmethyl)acetamide, α-lactam (1-acetyl-3,3-diphenylaziridin-2-one, as a 1:1 complex with 2,4-dinitroaniline) and aniline derivatives.
- Golub, Tatiana,Becker, James Y.
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experimental part
p. 3906 - 3912
(2012/06/04)
-
- Unusual behavior in the reactivity of 5-substituted- 1H-tetrazoles in a resistively heated microreactor
-
The decomposition of 5-benzhydryl-1H-tetrazole in an N-methyl-2- pyrrolidone/acetic acid/water mixture was investigated under a variety of high-temperature reaction conditions. Employing a sealed Pyrex glass vial and batch microwave conditions at 240 °, the tetrazole is comparatively stable and complete decomposition to diphenylmethane requires more than 8 h. Similar kinetic data were obtained in conductively heated flow devices with either stainless steel or Hastelloy coils in the same temperature region. In contrast, in a flow instrument that utilizes direct electric resistance heating of the reactor coil, tetrazole decomposition was dramatically accelerated with rate constants increased by two orders of magnitude. When 5-benzhydryl-1H-tetrazole was exposed to 220 ° in this type of flow reactor, decomposition to diphenylmethane was complete within 10 min. The mechanism and kinetic parameters of tetrazole decomposition under a variety of reaction conditions were investigated. A number of possible explanations for these highly unusual rate accelerations are presented. In addition, general aspects of reactor degradation, corrosion and contamination effects of importance to continuous flow chemistry are discussed.
- Gutmann, Bernhard,Glasnov, Toma N.,Razzaq, Tahseen,Goessler, Walter,Roberge, Dominique M.,Kappe, C. Oliver
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supporting information; experimental part
p. 503 - 517
(2011/06/28)
-
- Synthesis of α,α-diarylacetamides from benzyl aryl ketones using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate
-
Benzyl aryl ketones reacted with 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP, 1) to give migratory amidated compounds, which were transformed into the corresponding diarylacetamides by treating with LiAlH 4.
- Kitamura, Mitsuru,Miyagawa, Satoshi,Okauchi, Tatsuo
-
experimental part
p. 3158 - 3161
(2011/06/28)
-
- Oxidative conversion of α,α-disubstituted acetamides to corresponding one-carbon-shorter ketones using hypervalent iodine (λ5) reagents in combination with tetraethylammonium bromide
-
(Chemical Equation Presented) α,α-Disubstituted acetamides undergo oxidative dehomologation to give one-carbon-shorter ketones when reacted with a hypervalent iodine (λ5) reagent in combination with tetraethylammonium bromide (TEAB) in various solvents. In further studies, one such combination of a hypervalent iodine (λ5) reagent, o-iodoxybenzoic acid, and TEAB has been established as a new, mild, efficient, and general method for the transformation.
- Bellale, Eknath V.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
-
supporting information; experimental part
p. 9473 - 9475
(2009/04/06)
-
- ATM AND ATR INHIBITOR
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The present invention relates to a urea compound of formula (1) and a pharmaceutically acceptable salt thereof having inhibitory activity of ATM and ATR. According to the present invention, the urea compound of formula (1) selectively binds to ATM and ATR, and thus specifically suppresses the function of ATM and ATR as protein kinase. Therefore, the urea compound according to the present invention can be used for controlling cell function and treating diseases, in connection with function abnormality in ATM and ATR
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Page/Page column 31
(2008/06/13)
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- Anodic oxidation of benzil hydrazones in the presence of halide ions
-
Benzil hydrazones were subjected to electrolytic oxidation in MeOH containing halide ion source, such as KI and KBr. The results show that the reaction products were dependent on both the electrolytes and the substituents. In the presence of KI, benzoylphenyldiazomethanes were obtained, whereas in the presence of KBr, benzil dimethyl acetals were obtained.
- Okimoto, Mitsuhiro,Takahashi, Yukio
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p. 2059 - 2060
(2007/10/03)
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- Polyethylene glycol mediated reductive decyanation of diphenylacetonitrile moderately enhanced by microwave heating
-
An efficient and clean procedure for the preparation of alkyldiphenylmethanes and 4,4-diphenylbutylamines from their corresponding nitriles by using sodium hydroxide-polyethylene glycol reagent system in a domestic microwave oven is described. The products are isolated by simple aqueous work up in excellent yields.
- Bendale,Chowdhury,Khadilkar
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p. 433 - 435
(2007/10/03)
-
- Selective hydrolysis of nitriles to amides using NaOH-PEG under microwave irradiation
-
We describe here an efficient, rapid and selective method for the conversion of nitriles in to their corresponding amides in the presence of PEG-400, aqueous sodium hydroxide system under microwave irradiation.
- Bendale, Pravin M.,Khadilkar, Bhushan M.
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p. 1713 - 1718
(2007/10/03)
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- N-acylbenzotriazoles: Neutral acylating reagents for the preparation of primary, secondary, and tertiary amides
-
Readily available N-acylbenzotriazoles 2a-q efficiently acylate aqueous ammonia and primary and secondary amines to give primary, secondary, and tertiary amides in good to excellent yields. The wide applicability of the procedure is illustrated by the preparation of (i) α-hydroxyamides from α-hydroxy acids and of (ii) perfluoroalkylated amides.
- Katritzky,He,Suzuki
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p. 8210 - 8213
(2007/10/03)
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- Mild hydrolysis or alcoholysis of amides. Ti(IV) catalyzed conversion of primary carboxamides to carboxylic acids or esters
-
Reaction of primary amides (e.g., 1a or 6-13) or O-methylhydroxamates (1b and 1c) with a catalytic amount of TiCI4 and one equivalent of aqueous HCI converts these compounds in good yields to carboxylic esters (when an alcohol is used as solvent) or to carboxylic acids (when 9:1 dioxane:H2O is used as solvent). These conversions are chemoselective for primary amides: mono- and dialkyl amides are not affected by the reaction conditions. The hydrolysis conditions described do not compromise the stereochemical integrity of an adjacent chiral center. This is exemplified by the hydrolysis of naproxen amide (34) to naproxen (33) without detectable racemization as determined by chiral HPLC.
- Fisher,Caroon,Stabler,Lundberg,Zaidi,Sorensen,Sparacino,Muchowski
-
p. 142 - 145
(2007/10/02)
-
- O-Methylarenehydroxamates as Ortho-Lithiation Directing Groups. Ti(III)-Mediated Conversion of O-Methyl Hydroxamates to Primary Amides
-
Reaction of O-methyl benzohydroxamates 2a-c with sec-butyllithium in the presence of TMEDA at -40 deg C regiospecifically generates the highly reactive N,ortho-dilithiated species (e.g. 3).These dilithio species react avidly with a wide spectrum of electrophilic reagents, including alkyl halides, givind adducts which on reduction with TiCl3 are converted into ortho-substituted primary benzamides in excellent yields.Ortho lithiation of O-methyl benzohydroxamates is thus formally equivalent to ortho lithiation of primary benzamides themselves.The utility of these synthetic operations is enhanced by the well-known facility with wich the primary amide moiety can be transformed into other useful functional groups.The conversion of O-methyl hydroxamates to primary amides is shown to be general, as exemplified by transformation of 14a-f to 15a-f.O-Methyl-2-methylbenzohydroxamate (4a) undergoes regiospecific dilithiation on nitrogen and on the methyl group when treated with sec-butyllithium at -70 deg C.These dilithio species react with DMF or "Weinreb-type" amides to give condensation products wich cyclize to N-methoxyisoquinolin-1(2H)-ones under mildly acidic conditions.Removal of the N-methoxy moiety under conditions analogous to those used for O-methyl benzohydroxamate provides N-unsubstituted isoquinolin-1(2H)-ones with high overall efficiency.This process is exemplified by the synthesis of isoquinolin-1(2H)-one 9a, its 3-n-butyl congener 9b, and the tricyclic isoquinolin-1(2H)-ones 20a and 20b from O-methyl 2-methylbenzohydroxamate (4a).
- Fisher, Lawrence E.,Caroon, Joan M.,Jahangir,Stabler, S. Russell,Lundberg, Scott,Muchowski, Joseph M.
-
p. 3643 - 3647
(2007/10/02)
-
- The mechanism of the reaction of diphenylketene with bases in aqueous solution: Nucleophilic attack versus general base catalysis of ketene hydration
-
Diphenylketene was generated in aqueous solution by flash photolysis, and rates of its decay accelerated by 30 bases of various structure were determined. The rate constants so obtained did not show the regular dependence on basic strength expected if the bases were serving as general base catalysts assisting the attack of water on the ketene, but they did vary with polarizability and steric bulk of the base in the way expected for direct nucleophilic attack of the base on the carbonyl carbon atom of the ketene. Assignment of a direct nucleophilic role to the bases is supported by the formation of amide products in addition to diphenylacetic acid in the reaction of diphenylketene accelerated by ammonia and morpholine, and quantitative analysis of the product ratios shows that these two bases serve only as nucleophiles and that the diphenylacetic acid is formed by uncatalyzed reaction of diphenylketene with solvent water.
- Andraos,Kresge
-
p. 5643 - 5646
(2007/10/02)
-
- Experimental and Theoretical Study of the Reactivity of Primary and Secondary Enaminones toward Diphenylketene. A Comparison of AM1 and HAM/3 Semiempirical Methods
-
Diazodiphenylethanone (1) reacts with acyclic enamino ketones 2 and enamino esters 3 to form products of electrophilic attack of diphenylketene at Cα (5) and nitrogen (6 and 7).The relative reactivity of the different enaminones was shown to be consistent with HOMO energies determined by the HAM/3 semiempirical method.However, this approach could not completely explain the reactivity of the cyclic enamino ketones 4, which, by HAM/3, show a high energy second HOMO corresponding to the nonbonded pair of electrons on oxygen.
- Eberlin, Marcos N.,Takahata, Yuji,Kascheres, Concetta
-
p. 5150 - 5155
(2007/10/02)
-
- Dihydropyridine compounds having 1,4,4-trisubstitution useful as antihypertensive agents
-
Dihydropyridine compounds having 1,4,4-trisubstitution of the following formula (I): STR1 wherein R is one of --COR3, R3 being a group such as phenyl or benzyl; R4 where R4 is a heterocycle; --(CH2)n NR5 R6, with R5 and R6 being alkyl or joined to define a ring; or --(CH2)n COOR7, with R7 being alkyl or benzyl. R1 and R2 are alkyl, phenyl or substituted phenyl. The compounds are useful for the treatment of hypertension in mammals, e.g., in humans.
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-
- ORGANOPHOSPHORUS COMPOUNDS XXXIX. THE ACTION OF ALKYL PHOSPHITES ON OXAZOLIDINEDIONES. A NOVEL SYNTHESIS OF CARBAMIC ACID DERIVATIVES
-
Depending upon the experimental conditions trimethyl-, triethyl-, and triisopropyl phosphites react with oxazolidinedione (1a) ti give acid 2a and/or the corresponding alkyl ester 2b, c.Phenylacetamide (3) is also formed in a small amount.On the other hand, trialkyl phosphites cause the quantitative conversion of dione 1b into diphenylacetamide.The identity of the new compounds is established from analytical, chemical and spectroscopic evidence.
- Sidky, M. M.,El-Kateb, A. A.,Mahran, M. R.,Hennawy, I. T.,El-Malek, H. A. Abd
-
-
- REACTION OF BENZILMONOHYDRAZONE WITH S4N4, A CORRECTION
-
Reaction of benzilmonohydrazone (1) with S4N4 gives the azine (6) and not the 2-H-imidazole (2); this invalidates the claim that (2) is not the intermediate in the formation of N-benzoyltriphenylimidazole from benzil and ammonia.S4N4 converts diphenylketene into thiobenzophenone.
- Daley, Stephen T. A. K.,Rees, Charles W.
-
p. 1759 - 1760
(2007/10/02)
-
- Mechanism of the Reaction of Nitriles with Alkaline Hydrogen Peroxide. Reactivity of Peroxycarboximidic Acid and Application to Superoxide Ion Reaction
-
Formation of peroxycarboximidic acid (1) is not rate-determining in the reaction of nitrile with alkaline hydrogen peroxide to form amide and oxygen; the yield of amide based on H2O2 varies from 20 to 60percent.When dimethyl sulfoxide (DMSO), a reactive substrate, is added, the rate is independent of and governed in turn by a rate-determining addition of HOO- to nitrile.This reaction gives a reliable α-value of kHOO-/kHO-, which is 10000 for benzonitrile.A facile conversion of nitrile to amide may be achieved by the reaction in the presence of DMSO, unacco mpanied by side reactions such as the epoxyamide formation from α,β-unsaturated nitrile.Kinetics and product analysis suggest that a predominant reaction is not a non-radical oxidation of H2O2 with 1 but a radical decomposition of H2O2 which is induced by the homolysis of anion of 1 (1A).No singlet oxygen could be trapped chemically.The reaction of superoxide ion, O2-., with acetonitrile is shown to be analogous to that of HOO-; the decomposition of O2-. is fast in the presence of MeCN and DMSO in benzene, affording acetamide and dimethyl sulfone.
- Sawaki, Yasuhiko,Ogata, Yoshiro
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p. 793 - 799
(2007/10/02)
-