- (Ar-tpy)RuII(ACN)3: A Water-Soluble Catalyst for Aldehyde Amidation, Olefin Oxo-Scissoring, and Alkyne Oxygenation
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The synthetic chemists always look for developing new catalysts, sustainable catalysis, and their applications in various organic transformations. Herein, we report a new class of water-soluble complexes, (Ar-tpy)RuII(ACN)3, utilizing designed terpyridines possessing electron-donating and -withdrawing aromatic residues for tuning the catalytic activity of the Ru(II) complex. These complexes displayed excellent catalytic activity for several oxidative organic transformations including late-stage C-H functionalization of aldehydes with NH2OR to valuable primary amides in nonconventional aqueous media with excellent yield. Its diverse catalytic power was established for direct oxo-scissoring of a wide range of alkenes to furnish aldehydes and/or ketones in high yield using a low catalyst loading in the water. Its smart catalytic activity under mild conditions was validated for dioxygenation of alkynes to highly demanding labile synthons, 1,2-diketones, and/or acids. This general and sustainable catalysis was successfully employed on sugar-based substrates to obtain the chiral amides, aldehydes, and labile 1,2-diketones. The catalyst is recovered and reused with a moderate turnover. The proposed mechanistic pathway is supported by isolation of the intermediates and their characterization. This multifaceted sustainable catalysis is a unique tool, especially for late-stage functionalization, to furnish the targeted compounds through frequently used amidation and oxygenation processes in the academia and industry.
- Joarder, Dripta De,Gayen, Subrata,Sarkar, Rajarshi,Bhattacharya, Rajarshi,Roy, Sima,Maiti, Dilip K.
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p. 8468 - 8480
(2019/07/03)
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- Methyl esters of 2-(N-hydroxycarbamimidoyl)benzoyl-substituted α-amino acids as promising building blocks in peptidomimetic synthesis: a comparative study
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Abstract: An efficient and simple synthetic protocol for the synthesis of a number methyl esters of 2-(N-hydroxycarbamimidoyl)benzoyl-substituted (S)-α-amino acids via subsequent coupling and hydroxyamination of 2-cyanobenzamide derivatives has been developed. Comparative analysis of three pseudopeptide series based on 2-cyano- and 2-amidoxime-substituted benzoic acid and its pyridine and pyrazine counterparts has been provided and it has revealed a practical advantage of the benzoic acid derivatives due to their greater availability. The impact of the nitrogen atom in the aromatic ring on the trans/cis-amide equilibrium in the proline derivatives is discussed. Graphical abstract: [Figure not available: see fulltext.]
- Tkachuk, Volodymyr A.,Hordiyenko, Olga V.,Omelchenko, Irina V.,Medviediev, Volodomir V.,Arrault, Axelle
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p. 2293 - 2309
(2018/11/02)
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- 2-[2-(2-methoxyl phenoxyl) ethylamino]-3-aryl-4-quinazolinones compound and application thereof
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The invention belongs to the technical field of medicines, and relates to a 2-[2-(2-methoxyl phenoxyl) ethylamino]-3-aryl-4-quinazolinones derivative and application thereof. The 2-[2-(2-methoxyl phenoxyl) ethylamino]-3-aryl-4-quinazolinones derivative comprises a stereisomer of the compound and pharmacologically applicable salt. The general structural formula is as follows: as shown in the description, wherein R is as described in claims and the description. The 2-[2-(2-methoxyl phenoxyl) ethylamino]-3-aryl-4-quinazolinones derivative and salt formed by addition of a pharmacologically applicable acid of the compound can be combined with an existing medicine or used independently to form an influenza virus inhibitor which is used for treating influenza and particularly has a relatively curative effect on various types of influenza A.
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Paragraph 0047; 0048
(2018/03/25)
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- 2-[3-(4-morpholinyl)propylamine]-3-aryl-4-quinolinone compounds and application thereof
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The invention belongs to the technical field of medicines and relates to 2-[3-(4-morpholinyl)propylamine]-3-aryl-4-quinolinone compounds and an application thereof. 2-[3-(4-morpholinyl)propylamine]-3-aryl-4-quinolinone derivatives comprise stereisomers and pharmaceutically applicable salts of the compounds and have the general structural formula shown in the description, wherein R is described inthe claims and description. The 2-[3-(4-morpholinyl)propylamine]-3-aryl-4-quinolinone derivatives and pharmaceutically applicable acid-added salts of the compounds can be combined with existing medicines or used separately to serve as influenza virus inhibitors to treat influenza and have better curative effects on various type-A influenza in particular.
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Paragraph 0040; 0046
(2018/04/21)
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- Phthalocyanine green pigment fine clean production process
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The invention discloses a fine clean production process of a phthalocyanine green pigment. The fine clean production process comprises the following steps: (1) phthalonitrile preparation; (2) copper source preparation; (3) solvent selection; (4) copper phthalocyanine obtaining; (5) phthalocyanine green crude product preparation; (6) phthalocyanine green refining; (7) finished phthalocyanine green preparation; (8) finished phthalocyanine green crystal form change. The phthalocyanine green pigment produced by the production process is clean, environment-friendly and less in side reaction; the coloring power, the brightness, the dispersibility, the transparence and other properties are finally improved; the production process is strong in operability, close in step combination and short in process time.
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Paragraph 0027
(2016/12/22)
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- Preparation of highly potent and selective non-peptide antagonists of the arginine vasopressin V1A receptor by introduction of a 2-ethyl-1H-1-imidazolyl group
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To find a new series of arginine vasopressin (AVP) V1A receptor antagonists, the influence of the 2-phenyl group of 2-phenyl-4′-[(2,3,4,5- tetrahydro-1H-1-benzazepin-1-yl)carbonyl]benzanilide (7) was investigated. Replacement of the 2-phenyl group by a 2-ethyl-1H-imidazol-1-yl group was effective in yielding a V1A-selective compound. Moreover, this imidazolyl group was introduced in the same position in YM-35471 (6), and further studies of these compounds were performed. Consequently, we found that the (Z)-4′-({4,4-difluoro-5-[(N-cyclo-propylcarbamoyl) methylene]-2,3,4,5-tetrahydro-1H-1-benzazepin-1-yl}carbonyl)-2-(2-ethyl-1H-1- imidazol-1-yl)benzanilide (9f) exhibited highly potent affinity and selectivity, and was the most potent antagonist for the V1A receptor among our compounds. The synthesis and pharmacological evaluation of these compounds are described in this paper
- Shimada, Yoshiaki,Akane, Hiroaki,Taniguchi, Nobuaki,Matsuhisa, Akira,Kawano, Noriyuki,Kikuchi, Kazumi,Yatsu, Takeyuki,Tahara, Atsuo,Tomura, Yuichi,Kusayama, Toshiyuki,Wada, Koh-Ichi,Tsukada, Junko,Tsunoda, Takashi,Tanaka, Akihiro
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p. 764 - 769
(2007/10/03)
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- Effects of inorganic ions on rate of alkaline hydrolysis of phthalimide in the presence of cationic micelles
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Pseudo-first-order rate constants (kobs) for alkaline hydrolysis of phthalimide (PTH) show a monotonic decrease with the increase in the total concentration of cetyltrimethylammonium bromide ([CTABr]T) at a constant [NaOH] and [NaBr]. The pseudophase micellar (PM) model and the pseudophase ion-exchange (PIE) model reveal that the rate of alkaline hydrolysis of PTH is insignificant in the micellar pseudophase compared to that in the aqueous pseudophase under different reaction conditions. The CTABr micellar binding constants (KS) of ionized phthalimide (S-) follow an empirical relationship: KS = KS0/(1 + Ψ[MX]) where MX represents NaOH or NaBr. The value of the empirical parameter Ψ for HO- is nearly 30-fold smaller than that for Br-. The decrease in KS with the increase in [HO-] or [Br-] is attributed to the expulsion of S- ions from the micellar pseudophase to the aqueous pseudophase by HO- or Br-. Pseudo-first-order rate constants (kobs) for alkaline hydrolysis of PTH in the presence of CTABr micelles vary with [MX] (MX = NaBr, KCl and Na2CO3) according to the empirical relationship: kobs = (kobs0 + θK[MX])/(1 + K[MX]) where θ and K are empirical parameters. Based upon the values of θ, it is concluded that the respective anions Br-, Cl-, and CO32- can expel nearly 100, 60 and 15% of the total amount of micellized S- from the micellar pseudophase to the aqueous pseudophase under the limiting conditions where 1 ? K[MX].
- Khan, Mohammad Niyaz,Arifin, Zainudin
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p. 2503 - 2510
(2007/10/03)
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- Effect of CH3CN-H2O and CH3CN solvents on rate of reaction of phthalimide with piperidine
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Pseudo-first-order rate constants (kobs) for the reaction of piperidine with phthalimide vary linearly with the total concentration of piperidine ([Pip]T) at a constant content of CH3CN in H2O-CH3CN solvents within the CH3CN content range 2-80 % (v/v). The change in kobs with the change in [Pip]T at 100% (v/v) CH3CN obeys the relationship kobs = Ψ [Pip]T2/(1 + Φ [Pip]T). Copyright John Wiley & Sons, Ltd.
- Khan, M. Niyaz
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p. 187 - 193
(2007/10/03)
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- Phthalimidomethyl as a drug pro-moiety. Probing its reactivity
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Phthalimidomethyl derivatives 1, encompassing a wide range of leaving group abilities, are rapidly hydrolysed to the corresponding phthalamic acid via rate-determining attack at the phthalimide carbonyl group.
- Iley, Jim,Calheiros, Teresa,Moreira, Rui
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p. 955 - 958
(2007/10/03)
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- Tetrahydrophthalamide derivative, intermediate for producing the same, production of both, and herbicide containing the same as active ingredient
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The present invention relates to 3,4,5,6-tetrahydrophthalamide derivatives and 3,4,5,6-tetrahydroisophthalimide derivatives having excellent effects as effective active ingredients of herbicides, and processes for preparing the same, and provides the compounds having a more efficient herbicidal activity, and efficient and industrial processes for the preparation thereof. More specifically, the tetrahydrophthalimide derivative obtained by reacting a halogen-substituted 5-cycloalkyloxyaniline derivative with a 3,4,5,6-tetrahydrophthalic anhydride, or the tetrahydroisophthalimide derivative of the present invention is reacted with various types of amines to prepare a tetrahydrophthalamide derivative represented by the general formula (I): STR1 These tetrahydrophthalamide derivatives and the tetrahydroisophthalimide derivatives exhibit excellent herbicidal activities in the soil treatment in the paddy field and field and the stem-foliar treatment. The tetrahydroisophthalimide derivatives are also useful as intermediates for the preparation of the tetrahydrophthalamide derivatives, etc.
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- Heteroatom-Directed Metalation. Lithiation of N-Propenylbenzamides and N-Propenyl-o-toluamides. Novel Routes to Ortho-Substituted Primary Benzamide Derivatives and N-Unsubstituted Isoquinolin-1(2H)-ones
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Reaction of N-propenylbenzamides 4 and 9, obtained by LDA-induced isomerization of the corresponding N-allylbenzamides, 1, 8, and 14, with 2 equiv of sec-butyllithium or tert-butyllithium at low temperature regiospecifically generates the highly reactive N,ortho-dilithiated species (e.g., 5 and 17).These dilithio species react avidly with a wide spectrum of electophilic reagents, including alky halides, giving adducts which on hydrolysis with warm 50percent aqueous acetic acid are converted into ortho-substituted primary benzamides in excellent yields.Ortho-lithiation of N-propenylbenzamides is thus formally equivalent to ortho-lithiation of primary benzamides themselves.The utility of this important, previously unknown, synthetic operation is enhanced by the well-known facility with which the primary amide moiety can be transformed into other useful functional groups, as exemplified by the synthesis of 2-methoxy-6-methylbenzoic acid (12) and 2-methoxy-6-methylbenzonitrile (13) from N-propenyl-2-methoxybenzamide (9).N-Propenyl-o-toluamide (7) undergoes regiospecific dilithiation on nitrogen and on the methyl group under conditions analogous to those used for the N-propenylbenzamides.These dilithio species react with DMF or "Weinreb type" amides to give condensation products which cyclize to N-propenylisoquinolin-1(2H)-ones under mildly acidic conditions.Removal of the N-propenyl moiety under more strongly acidic conditions provides N-unsubstituted isoquinolin-1(2H)-ones with high overall efficiency.This process is exemplified by the synthesis of isoquinolin-1(2H)-one (23) and its 3-n-butyl congener 26 from N-propenyl-2-methylbenzamide (7).
- Fisher, Lawrence E.,Muchowski, Joseph M.,Clark, Robin D.
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p. 2700 - 2705
(2007/10/02)
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- AMMONOLYSIS OF CYCLIC IMIDES OF AROMATIC ACIDS
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In cyclic imides of aromatic di-and tetracarboxylic acids ammonolysis with the opening of the ring goes readily in water, but it does not go in anhydrous aprotic solvents.Quantum-chemical calculations of model compounds by the MINDO/3 method suggest the possibility of activation in an aqueous-alkaline medium as a result of the tautomeric transformation of the imide into the imidol, which has higher electrophilic reactivity.Here the transfer of a proton goes as a two-stage process on account of the successive participation of anions and molecules of water in the reaction.
- Arkhipova, i. A.,Gabdrakipov, V. Z.,Shalabaeva, I. D.,Zhubanov, B. A.
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p. 535 - 540
(2007/10/02)
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- Kinetics and Mechanism of Aminolysis of Phthalimide and N-Substituted Phthalimides. Evidence for the Occurrence of Intramolecular General Acid-Base Catalysis in the Reactions of Ionized Phthalimides with Primary Amines
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The kinetics and mechanism of the reactions of propane-1,3-diamine (PDA) and 1,4-diazabicyclooctane (DABCO) with phthalimide (PTH), N-hydroxyphthalimide (NHPH), and N-bromopropylphthalimide (NBPPH) and 2-methoxyethylamine with NHPH and NBPPH are described.Both ionized and non-ionized PTH are reactive toward PDA while only ionized NHPH showed reactivity toward PDA and 2-methoxyethylamine under the experimental conditions imposed.The presence and absence of or weak nucleophilic reactivity of DABCO toward neutral and ionized imides, respectively, are noted for PTH and NHPH.Significant nucleophilic reactivity of primary amines and the absence or considerably low nucleophilic reactivity of DABCO toward ionized PTH and NHPH are attributed to the occurence of intramolecular general acid-base (GA-GB) catalysis due to the presence of a mobile proton at the nucleophilic site of the nucleophile.This intramolecular GA-GB catalysis seems to decrease with increased steric requirements of the leaving group.Diffusion-controlled trapping stepwise and preassociation stepwise mechanisms are suggested in the aminolysis of non-ionized phthalimides and ionized phthalimides, respectively.Intermolecular GA and GB catalysis has been detected in the reactions of PDA and 2-methoxyethylamine with ionized NHPH and 2-methoxylethylamine with NHPH and ionized NHPH, respectively.Specific-base catalysis could be detected in the reactions of 2-methoxyethylamine with ionized NHPH.The reactions of monoprotonated PDA with ionized NHPH reveal few of favourable electrostatic effects.
- Khan, Mohammad Niyaz
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p. 435 - 444
(2007/10/02)
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- Process for preparing [1S-[1α,2α)Z),3α,4α]]-7-[3-[[[[[1-oxoheptyl]-amino]acetyl]amino]methyl]-7-oxabicyclo-[2,2,1]hept-2-yl]-5-heptenoic acid
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A new process for preparing [1S-[1α,2α(Z),-3α,4α]]-7-[3-[[[ (1-oxoheptyl)amino]acetyl]amino]-methyl]-7-oxabicyclo[2,2,1]hept-2-yl]-5-heptenoic acid. New intermediates are also described. [1S-(1α,2α(Z),3α,4α]]-7-[3-[[[[(1-oxoheptyl)-amino]acetyl]amino]methyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid is useful in the treatment of thrombotic disease.
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- Hypolipidemic activity of phthalimide derivatives V: Reduced and hydrolytic products of simple cyclic imides
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A series of cyclic imides and related compounds have previously been shown to possess hypolipidemic activity at the low dose level of 20 mg/kg/d. Hydrolytic and reduced products of the cyclic imides were synthesized and examined to discern if possible metabolic products were the active chemical species of these hypolipidemic agents. Phthalimide proved to be the most active cyclic imide tested. Unfortunately, the new products did not, in general, improve hypolipidemic activity in rodents. The exceptions were piperidine which demonstrated improved hypotriglyceridemic activity, and 3,4,5,6-dibenzohomopiperidin-2-one, which demonstrated improved hypocholesterolemic activity compared to phthalimide.
- Chapman Jr.,Wyrick,Josee Voorstad,et al.
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p. 1482 - 1484
(2007/10/02)
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- Intramolecular Influence of a Carboxylic Function on Platinium Blue Synthesis. A systematic Study of Complexes Originating from Acid Amides
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The use of acid amide as ligand for obtaining platinium blue has been investigated.While blue compounds are generally obtained by using the hydrolysis product of cis-dichlorodiammineplatinum(II) as platinum surce, with such ligands the reaction occurs very readily using potassium tetrachloroplatinate(II).The role of the carboxylic function which offers here a primary ligating site to platinum is evidenced.The compounds obtained have been characterized by UV-visible spectral measurments, Ce(IV) oxydative titration , ESR spectroscopy, and magnetic properties.Antitumoral activity toward leukemia L1210 and sarcoma 180 is reported for two of thesecompounds.As a first step for this antitumor study, these compounds have been found to be inactive toward Leukemia while they presnt intersting activity toward Sarcoma.
- Arrizabalaga, Philippe,Castan, Paule,Laurent, Jean-Pierre
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p. 4814 - 4818
(2007/10/02)
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- NMR STUDIES ON IMIDINES. III. (1)H AND (13)C NUCLEAR MAGNETIC RESONANCE STUDY ON THE TAUTOMERISM AND GEOMETRICAL ISOMERISM OF 3-IMINOISOINDOLINONE AND SOME ALKYLATED DERIVATIVES. OBSERVATION OF E AND Z ISOMERS ABOUT A FREE IMINO GROUPING
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3-Iminoisoindolinone (1) and some N-alkyl derivatives (8, 9, 10, 11, 12, 16 and 17) have been fully examined by (1)H and (13)C NMR spectroscopy. 3-(Methylimino)isoindolinone (12) cannot be obtained by reaction of 1 with methylamine, because it rearranges to 3-imino-2-methylisoindolinone (11), which reacts further to 2-methyl-3-(methylimino)isoindolinone (10).Both compounds have been shown to adopt the E configuration predominantly (88 percent for 11 at -55 deg C (CDCl3); 100 percent for 10). 3-(Methylimino)isoindolinone (12) favours the Z configuration (96 percent). Analogous results are found for the butyl derivatives (16, 17). 3-Imino isoindolinone (1) is present as the imino tautomer for 70 percent in DMSO-d6 solution as established by comparison of (13)C NMR chemical shift values of 1 with those of model compounds, 3-imino-2-methyl isoindolinone (11) and 3-(dimethylamino)isoindolinone (8).The tautomeric equilibrium is more extreme towards the imino form for the N-methyl and N-butyl derivatives 12 and 16. 2,3,4,5-tetrahydroisoindolinopyrimidin-6-one served as the imino model compound together with 10. (1)H and(13)C NMR data are given for several phthalic acid derivatives.
- Spiessens, Luc I.,Anteunis, Marc J. O.
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p. 965 - 994
(2007/10/02)
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- Hydrolysis Studies on Imidan
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Hydrolysis of imidan (I), a wide spectrum pesticide under basic and acidic conditions has been studied.The products such as N-mercaptomethylphthalimide (VI), N,N'-ethylenediphthalimide (VII) have been identified, besides some of the well known compounds and modes of hydrolysis determined.
- Kadam, A. N.,Ghatge, B. B.
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p. 460 - 461
(2007/10/02)
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- The Separation of Polar Steric Effects. Part 14. Kinetics of the Reactions of Benzoic Acid and of ortho-Substituted Benzoic Acids with Diazodiphenylmethane in Various Alcohols
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The main results now discussed are rate coefficients for the reactions of benzoic acid and 32 ortho-substituted benzoic acids with diazodiphenylmethane (DDM) at 30.0 deg C in 11 alcohols including 2-methoxyethanol.The reaction involves a rate-determining proton transfer.The results have been subjected to correlation analysis in two ways. (a) For the reactions of a given acid in the various alcohols, the log k values are correlated through multiple regression on appropriate solvent parameters. (b) For reactions in a given alcohol, the log k values for the various acids are correlated by using the appropriate form of the extended Hammett equation involving inductive, resonance, and steric parameters.Analyses of type (a), as in earlier work, involve the ?* value of the group R in the alcohol ROH, the Kirkwood function of dielectric constant, f(ε)=(ε-1)/(2ε+1) and nγH, the number of hydrogen atoms in the γ-position in the alcohol.These correlations yield information on the influence of ortho-substituents on the relative importance of specific and non-specific solvent effects.In analyses of type (b) the correlation equations are established with a limited set of substituents (up to 18), whose characteristic parameters ?I, ?R, and υ (determined by Charton) are well established, and are unlikely to show effects due to hydrogenbonding or substituent conformation.The results for other substituents are then interpreted by comparing log k(calc.) from a correlation expression with log k(obs.).
- Aslam, Hanif M.,Burden, Alan G.,Chapman, Norman B.,Shorter, John,Charton, Marvin
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p. 500 - 508
(2007/10/02)
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- Process for cleaving an imido side chain from penicillins and cephalosporins
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The amic acid group of a 7-(amic acid) cephalosporin or 6-(amic acid) penicillin is cleaved by dehydration to the corresponding novel 7-isoimidocephalosporin or 6-isoimido-penicillin, and cleavage of the 7-isoimidocephalosporin or 6-isoimidopenicillin to the corresponding 7-aminocephalosporin or 6-aminopenicillin or to a corresponding 7-acylamidocephalosporin or 6-acylamidopenicillin.
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- Oxadiazole benzoic acid derivatives as herbicides
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New 2-(1,3,4-oxadiazole-2-yl) benzoic acids and salts and esters thereof, as well as certain 2-(2-oxazolyl) benzoic acids, salts and esters, having the formula: SPC1 Where X is nitrogen or C-R" (R" being hydrogen or methyl), R is phenyl or various substituents, and R' and the Y's are hydrogen or various substituents, are effective preemergence or postemergence herbicides, on various crops. The chemicals act selectively and are useful against purple nutsedge and in cranberry. Oxadiazoles of the invention may be made by reacting a benzhydrazide with phthalic anhydride to form a hydrazide which is cyclized by removal of the elements of water, using as a catalyst fuming sulfuric acid or dimethylformamide-sulfur trioxide complex.
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