- Metabolism of the Insecticide Phoxim in Plants and Cell Suspension Cultures of Soybean
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The metabolism of phoxim (Z-α-imino>phenylacetonitrile), Volaton, was investigated using heterotrophic cell suspension cultures of soybean (Glycine max L.) and isolated organs (roots, stems, cotyledons, and leaves) of aseptically grown soybean plants.In both systems phoxim was first hydrolyzed to the corresponding oxime, which was then reduced to a primary nitrile amine.The primary amino group was N-malonylated as the terminal step of the catabolic sequence.The structure of this terminal metabolite was elucidated by spectroscopic (UV, IR, NMR, and MS) methods and chemical synthesis.In the plant no organ-specific differences in phoxim metabolism were observed.In the cell culture system phoxim was quantitatively converted to the N-malonate within 18-20 h, whereas in plant organs such extensive conversion could not be observed even within incubation times of about 5 days.The N-malonate was found to be excreted from the cultured cells into the medium; this effect could not be shown for the plant tissues.Keywords: Organothiophosphate metabolism; soybean plants and cell suspension cultures; conjugation reactions; N-malonylation; O-glucoside formation
- Hoehl, Hans-Ulrich,Barz, Wolfgang
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- Facile Access to 1,4-Disubstituted Pyrrolo[1,2- a ]pyrazines from α-Aminoacetonitriles
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An efficient and practical synthetic protocol for the synthesis of 1,4-disubstituted pyrrolo[1,2- a ]pyrazine derivatives is described that originates from α-substituted pyrroloacetonitriles which, in turn, are readily available from aryl and alkyl aldehydes. The α-pyrroloacetonitriles were subjected to a Friedel-Crafts acylation with methyl chlorooxoacetate followed by reduction of the nitrile group under Pd-catalyzed hydrogenation conditions and finally aromatization with DDQ leading to the desired pyrrolo[1,2- a ]pyrazine derivatives. This method was generalized and successfully applied to various aryl, heteroaryl, and alkyl substrates. The developed protocol provides direct and convenient access to 1,4-disubstituted ring systems in moderate to good overall yields (51-68percent) without the need for purification of the intermediates. Further functionalization via the stepwise halogenation (bromination, iodination) and nitration was also demonstrated. In addition, the potential of the ester functionality for elaboration was demonstrated by manipulating into heterocyclic ring systems, exemplified by conversion into benzoxazole derivatives.
- Basha, Mushkin,Belema, Makonen,Dhar, T. G. Murali,Gupta, Anuradha,Gupta, Arun Kumar,Indasi, Gopi Kumar,Karmakar, Ananta,Mathur, Arvind,Meanwell, Nicholas A.,Ramalingam, Sridharan,Rampulla, Richard
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supporting information
p. 441 - 449
(2020/01/23)
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- Discovery of N-Cyano-sulfoximineurea Derivatives as Potent and Orally Bioavailable NLRP3 Inflammasome Inhibitors
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NLRP3 inflammasome mediated release of interleukin-1β (IL-1β) has been implicated in various diseases. In this study, rationally designed mimics of sulfonylurea moiety were investigated as NLRP3 inhibitors. Our results culminated into discovery of series of unprecedented N-cyano sulfoximineurea derivatives as potent NLRP3 inflammasome inhibitors. Compound 15 (IC50 = 7 nM) and analogues were found to be highly potent and selective NLRP3 inflammasome inhibitor with good pharmacokinetic profile. These effects translate in vivo, as 15, 29, and 34 significantly inhibit NLRP3 dependent IL-1β secretion in mice.
- Agarwal, Sameer,Sasane, Santosh,Shah, Hardik A.,Pethani, Jignesh P.,Deshmukh, Prashant,Vyas, Vismit,Iyer, Pravin,Bhavsar, Harsh,Viswanathan, Kasinath,Bandyopadhyay, Debdutta,Giri, Poonam,Mahapatra, Jogeswar,Chatterjee, Abhijit,Jain, Mukul R.,Sharma, Rajiv
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supporting information
p. 414 - 418
(2020/03/13)
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- NOVEL COMPOUNDS FOR INHIBITION OF JANUS KINASE 1
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An object of the invention is to provide compounds as selective JAK1 inhibitor, a process for preparation of the inhibitors, a composition containing the compounds and utility of the compounds.
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Page/Page column 96
(2020/12/11)
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- Titanium-Catalyzed Cyano-Borrowing Reaction for the Direct Amination of Cyanohydrins with Ammonia
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α-Aminonitrile was an important building block in natural products and key intermedia in organic chemistry. Herein, the direct amination of cyanohydrins with the partner of ammonia to synthesis N-unprotected α-aminonitriles is developed. The reaction proceeds via titanium-catalyzed cyano-borrowing reaction, which features high atom economy and simple operation. A broad range of ketone or aldehyde cyanohydrins was tolerated with ammonia, and the N-unprotected α-aminonitriles were synthesis with moderate to high yields under mild reaction conditions.
- Li, Qing-Hua,Li, Zhao-Feng,Tao, Jing,Li, Wan-Fang,Ren, Li-Qing,Li, Qian,Peng, Yun-Gui,Liu, Tang-Lin
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supporting information
p. 8429 - 8433
(2019/10/14)
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- Photoreactive fused aziridinylpiperazines on the background of 4-substituted chalcones and their benzimidazolic analogs
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The reaction of bromo-substituted chalcones with various diamino-compounds leads to the fused heterocyclic products, aziridinylpiperazines, exhibiting photoreactivity in the crystalline state. Crystals of 4-nitrosubstituted compounds of this family change their color from yellowish to deep violet-blue, 4-cyanosubstituted ones – from yellowish to pink at UV irradiation. Discussion on the mechanism of this phototransformation is still in progress, however, several facts points to the free radial nature of the photogenerated colored semi-products stabilized only by crystalline state of the irradiated samples. Formation of a mixture of positional isomers at interaction of bromo-chalcones with asymmetric diamines of aliphatic/alicyclic or aromatic series at synthesis of the title compounds is of significant interest as well.
- Kotlyar, Volodymyr M.,Kolomoitsev, Oleksii O.,Nikolaievskyi, Dmytro V.,Pedan, Polina I.,Chumak, Andrii Yu,Orlov, Valery D.,Shishkina, Svitlana V.,Doroshenko, Andrey O.
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p. 741 - 746
(2019/01/10)
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- Gold-catalyzed oxidative couplings of two indoles with one aryldiazo cyanide under oxidant-free conditions
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Gold-catalyzed oxidative couplings of two indoles and one α-cyano gold carbene to form bis(indolyl)methane derivatives are described. Two different indoles are compatible with these reactions to provide reasonable yields. A plausible mechanism is postulated to rationalize the experimental data including product distributions, D2O labeling, and the significant effects of gold catalysts and cyano groups.
- Singh, Rahulkumar Rajmani,Liu, Rai-Shung
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supporting information
p. 4593 - 4596
(2017/04/28)
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- Gold-Catalyzed Oxidative [2+2+1] Annulations of Aryldiazo Nitriles with Imines To Yield Polyarylated Imidazolium Salts
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Gold-catalyzed oxidative [2+2+1] annulations between two imines and one α-cyano arylgold carbene afforded polyarylated imidazolium salts and molecular hydrogen efficiently. Control experiments suggest that the gold catalyst alone facilitates the main annulation, whereas Ag+ avoids the formation of inactive LAuCN. DFT calculations suggest that the success of this annulation relies on a 6 π-electrocyclization of cyano-free intermediates with cis-configured imines as initial reagents.
- Pawar, Samir Kundlik,Yang, Ming-Chung,Su, Ming-Der,Liu, Rai-Shung
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supporting information
p. 5035 - 5039
(2017/04/24)
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- Mechanochemical Strecker Reaction: Access to α-Aminonitriles and Tetrahydroisoquinolines under Ball-Milling Conditions
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A mechanochemical version of the Strecker reaction for the synthesis of α-aminonitriles was developed. The milling of aldehydes, amines, and potassium cyanide in the presence of SiO2gave the corresponding α-aminonitriles in good to high yields. The high efficiency of the mechanochemical Strecker-type multicomponent reaction allowed the one-pot synthesis of tetrahydroisoquinolines after a subsequent internal N-alkylation reaction.
- Hernández, José G.,Turberg, Mathias,Schiffers, Ingo,Bolm, Carsten
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p. 14513 - 14517
(2016/10/03)
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- Gold-catalyzed [3+2]-annulations of α-aryl diazonitriles with ynamides and allenamides to yield 1-amino-1H-indenes
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Gold-catalyzed [3+2]-annulations of α-aryl diazonitriles with ynamides and allenamides yield 1-amino-1H-indenes in two distinct pathways; the success of these annulations relies on the high electrophilicity of α-cyano arylgold carbenes to activate an ionic pathway.
- Singh, Rahulkumar Rajmani,Pawar, Samir Kundlik,Huang, Min-Jie,Liu, Rai-Shung
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supporting information
p. 11434 - 11437
(2016/09/23)
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- A Sustainable, Semi-Continuous Flow Synthesis of Hydantoins
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Hydantoins are an important class of heterocycles with applications in pharmacy, agriculture, and as intermediates in organic synthesis. Traditional synthetic procedures to access hydantoins are target oriented with multiple synthetic steps and often use reagents that are not commercially available or sustainable. Herein, an efficient process is described for accessing hydantoins starting from commercially available amines using consecutive gas–liquid transformations (oxygen, carbon dioxide). This semi-continuous process produced ten benzylic/aliphatic hydantoins in good overall yields (52–84 %).
- Vukeli?, Stella,Koksch, Beate,Seeberger, Peter H.,Gilmore, Kerry
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supporting information
p. 13451 - 13454
(2016/09/13)
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- Efficient asymmetric synthesis of 1-cyano-tetrahydroisoquinolines from lipase dual activity and opposite enantioselectivities in α-aminonitrile resolution
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Dual promiscuous racemization/amidation activities of lipases leading to efficient dynamic kinetic resolution protocols of racemic α-aminonitrile compounds are described. α-Amidonitrile products of high enantiomeric purity could be formed in high yields. Several lipases from different sources were shown to exhibit the dual catalytic activities, where opposite enantioselectivities could be recorded for certain substrates. Dynamic chemistry: Dual promiscuous racemization/amidation activities of lipases leading to efficient dynamic kinetic resolution protocols of racemic α-aminonitrile compounds are described. α-Amidonitrile products of high enantiomeric purity could be formed in high yields. Several lipases from different sources were shown to exhibit the dual catalytic activities, in which opposite enantioselectivities could be recorded for certain substrates (see scheme).
- Sakulsombat, Morakot,Vongvilai, Pornrapee,Ramstr?m, Olof
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supporting information
p. 11322 - 11325
(2014/10/15)
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- Continuous-flow oxidative cyanation of primary and secondary amines using singlet oxygen
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Primary and secondary amines can be rapidly and quantitatively oxidized to the corresponding imines by singlet oxygen. This reactive form of oxygen was produced using a variable-temperature continuous-flow LED-photoreactor with a catalytic amount of tetraphenylporphyrin as the sensitizer. α- Aminonitriles were obtained in good to excellent yields when trimethylsilyl cyanide served as an insitu imine trap. At 25°C, primary amines were found to undergo oxidative coupling prior to cyanide addition and yielded secondary α-aminonitriles. Primary α-aminonitriles were synthesized from the corresponding primary amines for the first time, by an oxidative Strecker reaction at -50 °C. This atom-economic and protecting-group-free pathway provides a route to racemic amino acids, which was exemplified by the synthesis of tert-leucine hydrochloride from neopentylamine. The mild synthesis of imines paves the way to aminonitriles and amino acids. Aerobic oxidation of primary and secondary amines in a continuous photoreactor with singlet oxygen generated insitu led to the rapid formation of imines, which were quantitatively trapped as α-aminonitriles (see scheme; TMS=trimethylsilyl). Benzylic and primary α-aminonitriles, precursors for amino acids, could be efficiently produced in three minutes.
- Ushakov, Dmitry B.,Gilmore, Kerry,Kopetzki, Daniel,McQuade, D. Tyler,Seeberger, Peter H.
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supporting information
p. 557 - 561
(2014/01/23)
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- TITANIUM COMPOUNDS AND PROCESS FOR CYANATION OF IMINES
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The present invention relates to titanium catalysts for synthesis reactions produced by bringing a reaction mixture comprising a titanium alkoxide and a ligand in contact with water, wherein the ligand is represented by the general formula (e): wherein R
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Page/Page column 20-21
(2012/01/13)
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- Bisheterocycle Tandem Compounds Useful as Antiviral Agents, the Uses Thereof and the Compositions Comprising Such Compounds
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The present invention provides small molecule compounds of bisheterocycle in tandem having the structural formula of P1-P2, and the use thereof as well as a composition containing the compounds, each of P1 and P2 is an unsaturated 5-member heterocyclic ri
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Page/Page column 20
(2009/01/20)
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- BISHETEROCYCLE TANDEM COMPOUNDS USEFUL AS ANTIVIRAL AGENTS, THE USES THEREOF AND THE COMPOSITIONS COMPRISING SUCH COMPOUNDS
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The present invention provides small molecule compounds of bisheterocycle in tandem having the structural formula of P1-P2, and the use thereof as well as a composition containing the compounds, each of P1 and P2 is an unsaturated 5-member heterocyclic ri
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Page/Page column 23
(2010/11/30)
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- Method of making imidazole-2-thiones
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The present invention provides a method of making an imidazole-2-thione which comprises the steps of reacting a vicinal diamine with a compound having a thiocarbonyl moiety and oxidizing the resulting reaction product to obtain said imidazole-2-thione.
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Page/Page column 6; 8
(2008/06/13)
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- Chemoenzymatic approaches to the dynamic kinetic asymmetric synthesis of aromatic amino acids
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Enzymatic approaches for the production of amino acids by nitrilases are described. Dynamic kinetic asymmetric synthesis conditions were established for the aromatic aminonitriles, phenylglycinonitrile and 4- fluorophenylglycinonitrile, at high pH to produce the corresponding amino acid products in high enantiomeric excess. N-Acylation of aromatic aminonitriles led to spontaneous racemization at pH 8, allowing preferential enzymatic hydrolysis of the (R)-enantiomer to afford the product N-acylamino acids in up to 99% enantiomeric excess (ee).
- Chaplin, Jennifer A.,Levin, Michael D.,Morgan, Brian,Farid, Nancy,Li, Jen,Zhu, Zuolin,McQuaid, Jeff,Nicholson, Lawrence W.,Rand, Cynthia A.,Burk, Mark J.
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p. 2793 - 2796
(2007/10/03)
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- Improved Reagent for Electrophilic Amination of Stabilized Carbanions
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(Equation presented) Enolate amination using O-di(p-methoxyphenyl) phosphinylhydroxylamine 2 is reported. Reagent 2 reacts efficiently with stabilized sodium or potassium enolates derived from malonates, phenylacetates, and phenylacetonitriles and is sufficiently soluble for use in solution at -78°C.
- Smulik, Jason A.,Vedejs, Edwin
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p. 4187 - 4190
(2007/10/03)
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- Zinc/ammonium formate: A new facile system for the rapid and selective reduction of oximes to amines
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Various oximes, both aldoximes and ketoximes, are selectively reduced to corresponding amines employing low cost zinc dust and ammonium formate despite presence of other functional groups such as halogens, -OH, -OCH3, -COOH, -CN, > C = C 3.
- Abiraj,Gowda, D. Channe
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p. 332 - 334
(2007/10/03)
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- Nitrilase from rhodococcus rhodochrous ncimb 11216
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The invention relates to nucleic acid sequences which code for a polypeptide having nitrilase activity, to nucleic acid constructs comprising the nucleic acid sequences, and to vectors comprising the nucleic acid sequences or the nucleic acid constructs. The invention further relates to amino acid sequences which are encoded by the nucleic acid sequences, and to microorganisms comprising the nucleic acid sequences, the nucleic acid constructs or vectors comprising the nucleic acid sequences or the nucleic acid constructs. The invention additionally relates to an enzymatic process for preparing carboxylic acids from the corresponding nitrites.
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- Lithium perchlorate mediated three component reaction for the preparation of primary amines
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In the presence of lithium perchlorate in diethyl ether, LPDE, a three- component reaction between aldehydes, sodium hexamethyldisilazane or lithium hexamethyldisilazane, LHMDS, and different nucleophiles proceeds smoothly to afford primary amines in good yields.
- Saidi, Mohammad R.,Javanshir, Shahrzad,Mojtahedi, Mohammad M.
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p. 330 - 331
(2007/10/03)
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- α-Aminonitrile hydration in the presence of hydrogen peroxide in aqueous basic medium
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α-Aminonitriles are hydrated into α-aminoamides in the presence of hydrogen peroxide in sodic or ammoniacal basic medium. While the hydration mechanism is close to the mechanism described previously in the case of aromatic nitrites, we showed that, in weakly basic conditions, the amine function of α-aminonitrile is competitively oxidized via a peroxyimidic acid by an intramolecular process. In the case of 2-aminopropanenitrile, this reaction leads to pyruvamide oxime. Furthermore, the study of structurereactivity relationships in the hydration of aliphatic and aromatic monofunctional nitriles and α-aminonitriles showed that the reactivity of the substrates towards hydroperoxide onion, which mostly depends on inductive effects of the substituents, is sufficiently enhanced to allow hydration of tertiary α-aminonitriles with low steric hindrance and regioselective hydration of dissymmetric α-aminodinitriles. Eisevier,.
- Taillades, Jacques
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- Influence of a Hydroalcoholic Solvent on the Enantioselectivity of α-Amino nitrile Hydration Catalysed by Chiral Ketones
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The enantioselective hydration of α-aminonitriles 1, RCH(CN)NH2 i; 1c: R = Ph> has been achieved in an alkaline hydroalcoholic medium in the presence of chiral ketonic catalysts.Of the different ketones used, (-)-(5R,3R,2R)-5-(methylethenyl)-3-cyano-2-methylcyclohexanone (8) gives rise to significant enantioselectivity D/kL = 2.1; T = 10 deg C; solvent, water-propan-2-ol (45:55,v/v)>.Although the structure of the catalyst could probably be improved, we show in this paper that the efficiency and especiallythe enantioselectivity of the catalyst are not only under steric control but also depend on the nature and composition of the hydroalcoholic solvent.Thus, for the three aminonitriles studied in the presence of the catalyst 8, the increase in percentage of propan-2-ol favours the hydration of the D α-aminonitrile as shown for the hydration of 1c for which the ratio kD/kL increases threefold when the percentage of propan-2-ol increases from 10 to 95percent.
- Lagriffoul, Pierre-Henri,Tadros, Ziad,Taillades, Jacques,Commeyras, Auguste
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p. 1279 - 1285
(2007/10/02)
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- Process for obtaining α-amino nitriles and their applications to organic synthesis
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The present invention relates to the synthesis of nitriles having an amine function on the adjacent carbon.
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- Useful Synthesis of α-Aminonitriles by Means of Alumina and Ultrasound
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Combined use of alumina and ultrasound facilitates the synthesis of α-aminonitriles under solid-liquid two phase conditions from carbonyl compounds, salts of amines and potassium cyanide in organic solvents.
- Hanafusa, Terukiyo,Ichihara, Junko,Ashida, Tetsuya
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p. 687 - 690
(2007/10/02)
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- PRIMARY AMINES VIA ELECTROPHILIC AMINATION OF ORGANOMETALLIC COMPOUNDS WITH O-(DIPHENYLPHOSPHINYL)HIDROXYLAMINE
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It is shown that O-(diphenylphosphinyl)hydroxylamine 4a transforms all kinds of "carbanions" into primary amines; best yields are received with "stabilized anions", e.g. of the benzylic type.
- Boche, Gernot,Bernheim, Michael,Schrott, Wolfgang
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p. 5399 - 5402
(2007/10/02)
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- Process for the manufacture of optically active, optionally substituted 2-amino-2-phenylacetic acid
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Optically active 2-amino-2-phenylacetic acid of the formula STR1 in which R1, R2 and R3, which are identical or different, denote hydrogen, halogen, hydroxy, alkyl, acyl, or alkoxy, is prepared by asymmetrical transformation of a corresponding DL-aminophenylacetonitrile with L(+)-tartaric acid. To this end the corresponding DL-2-amino-2-phenyl-acetonitrile is reacted with approximately equimolar amounts of L(+)-tartaric acid in the presence of at least one alkanol having from 1 to 5 carbon atoms and/or at least one carbonyl compound at a temperature of from 0° to 50° C. and the mixture is stirred for 2 to 120 hours at the indicated temperature. The crystallized transformation product is separated, hydrolyzed by treatment with an acid and the desired product is isolated.
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- Resolution of aminonitriles
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The present invention is a chemical method for obtaining an optically pure 2-aminonitrile or a 2-aminoamide from (1) an optically impure mixture, (2) a racemic mixture, or (3) the optically pure enantiomer of the opposite configuration, in an amount greater than actually present, by use of optically active acids with a ketone or an aldehyde catalyst. Yields of greater than 70 percent of one enantiomer are obtained from racemic mixtures in very short time periods.
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