- Pillar[5]arenes with an introverted amino group: A hydrogen bonding tuning effect
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Pillar[5]arenes with introverted amino groups were produced through aminolysis. X-ray analysis demonstrated that the intramolecular hydrogen bonding induced the amino group toward the inner space of the cavity. The kinetic studies and molecular modelings revealed that the hydrogen bonding also contributed to the acceleration of the aminolysis through stabilizing the intermediate.
- Chen, Lei,Li, Zhiming,Chen, Zhenxia,Hou, Jun-Li
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Read Online
- An NMR study on a pseudo-intramolecular transacylation reaction of an α-aryl-β-keto ester
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The pseudo-intramolecular transacylation reaction efficiently proceeds like an intramolecular reaction, even though it is actually an intermolecular reaction. We have obtained valuable insights by monitoring the reaction by 1H NMR spectroscopy.
- Hirai, Sho,Asahara, Haruyasu,Hirao, Shotaro,Sawayama, Jun,Sugimoto, Ryuichi,Saigo, Kazuhiko,Nishiwaki, Nagatoshi
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Read Online
- Decarboxylative Ritter-Type Amination by Cooperative Iodine (I/III)─Boron Lewis Acid Catalysis
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Recent years have witnessed important progress in synthetic strategies exploiting the reactivity of carbocations via photochemical or electrochemical methods. Yet, most of the developed methods are limited in their scope to certain stabilized positions in molecules. Herein, we report a metal-free system based on the iodine (I/III) catalytic manifold, which gives access to carbenium ion intermediates also on electronically disfavored benzylic positions. The unusually high reactivity of the system stems from a complexation of iodine (III) intermediates with BF3. The synthetic utility of our decarboxylative Ritter-type amination protocol has been demonstrated by the functionalization of benzylic as well as aliphatic carboxylic acids, including late-stage modification of different pharmaceutical molecules. Notably, the amination of ketoprofen was performed on a gram scale. Detailed mechanistic investigations by kinetic analysis and control experiments suggest two mechanistic pathways.
- Narobe, Rok,Murugesan, Kathiravan,Schmid, Simon,K?nig, Burkhard
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p. 809 - 817
(2022/01/15)
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- A novel construction of acetamides from rhodium-catalyzed aminocarbonylation of DMC with nitro compounds
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Dimethyl carbonate (DMC), an environment-friendly compound prepared from CO2, shows diverse reactivities. In this communication, an efficient procedure using DMC as both a C1 building block and solvent in the aminocarbonylation reaction with nitro compounds has been developed. W(CO)6acts both a CO source and a reductant here.
- Bao, Zhi-Peng,Miao, Ren-Guan,Qi, Xinxin,Wu, Xiao-Feng
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supporting information
p. 1955 - 1958
(2021/03/02)
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- Monoacylation of Symmetrical Diamines in Charge Microdroplets
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Monoacylation of symmetrical diamine is achieved when the primary α,ω-diamines (carbon numbers n = 3, 5 and 12) are diluted in ethyl acetate, and the resultant mixture is electrosprayed across a 10 mm distance in ambient air toward a mass spectrometer. The N-acylated product is formed in charged microdroplets without acidifying and activating agents and in the absence of heat. This result provided an insight into the orientation of the amines in the droplets, suggesting that the ester is activated to react with the amine at the droplet surface due to the high abundance of protons at the air-droplet interface.
- Ansu-Gyeabourh, Emelia,Amoah, Enoch,Ganesa, Chandrashekar,Badu-Tawiah, Abraham K.
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p. 531 - 536
(2021/01/13)
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- PRODUCTION METHOD OF AMIDE COMPOUND
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PROBLEM TO BE SOLVED: To provide a production method of an amide compound, which can use a variety of carboxylic acid halides and can produce a desired amide compound at a yield higher than a batch process by suppressing a side reaction. SOLUTION: Provided is a production method of an amide compound using a flow type reactor, in which the flow type reactor includes: a first flow path; a second flow path; a first mixing means provided at a confluent part of the first flow path and the second flow path; and a third flow path that is connected to the first mixing means and arranged on a down stream side of the first mixing means, the production method comprising: a mixing step of obtaining a mixed liquid by circulating a first liquid containing the carboxylic acid halide in the first flow path, circulating a second liquid containing an amine compound having a molecular weight of 1,000 or less, an inorganic alkali and water in the second flow path, and mixing the first liquid and the second liquid by the first mixing means to obtain a mixture; and a reaction step of obtaining an amide compound by circulating the mixed liquid in the third flow path and reacting the carboxylic acid halide and the amine compound in the third flow path. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2020,JPO&INPIT
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Paragraph 0018; 0089-0106
(2020/10/08)
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- Synthesis of diverse libraries of carboxamides via chemoselective N-acylation of amines by carboxylic acids employing Br?nsted acidic IL [BMIM(SO3H)][OTf]
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Chemoselective N-acylation of amines with carboxylic acids as acyl electrophiles and Br?nsted acidic IL [BMIM(SO3H)][OTf] as promoter is reported under both thermal and microwave irradiation to produce libraries of carboxamides in good to excellent yields after a simple workup. The protocol is compatible with structurally diverse 1° and 2° amines and works in the presence of sensitive functional groups such as thiols and phenols. The potential for recycling and reuse of the IL is also demonstrated.
- Savanur, Hemantkumar M.,Malunavar, Shruti S.,Prabhala, Pavankumar,Sutar, Suraj M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
(2019/09/30)
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- Metal-Free O-Selective Direct Acylation of Amino Alcohols Through Pseudo-Intramolecular Process
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Efficient α-aryl-β-keto ester acylation of amine accompanied by the elimination of ethyl phenylacetate was achieved owing to the pseudo-intramolecular process. The eliminated ethyl phenylacetate could be recycled by conversion into an α-aryl-β-keto ester upon treatment with an acyl chloride in the presence of lithium bis(trimethylsilyl)amide, by which the atom economy considerably increased. Acylation using an α-aryl-β-keto ester is highly sensitive to the bulkiness of the nucleophile, which facilitated the regioselective-acylation of the less hindered amino group in diamine without protecting the other. The transacylation of α-aryl-β-keto ester with N-alkylamino alcohol resulted in chemoselective O-acylation without protecting the amino group because the hydroxy group was attracted to the reaction site of the keto ester by forming an ammonium salt. Transacylation was demonstrated to be a practically useful tool for organic synthesis because this protocol can be conducted under mild conditions with simple manipulations in the absence of any additives such as metal catalyst and base.
- Yokoyama, Soichi,Shibauchi, Hiroshi,Asahara, Haruyasu,Nishiwaki, Nagatoshi
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supporting information
p. 1125 - 1133
(2019/02/01)
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- Efficient acylation and transesterification catalyzed by dilithium tetra-tert-butylzincate at low temperatures
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The acylation and transesterification of alcohols with vinyl acetate and carboxylic esters were investigated in the presence of a catalytic amount (1-10 mol %) of dilithium tetra-tert-butylzincate (TBZL) as a catalyst. The acylation proceeded quantitatively at 0 °C within 1 h. The transesterification occurred for a wide range of combinations of esters and alcohols at 0 to -40 °C. To the best of our knowledge, this is the first successful transesterification at such low temperatures. The time-conversion plots for the transesterification show that the reaction reached equilibrium within 5 min at 0 °C. The reaction proceeded quantitatively by addition of molecular sieves 4A. In addition, the transesterification proceeded even in the presence of H2O and amines.
- Oshimura, Miyuki,Oda, Yuki,Kondoh, Keita,Hirano, Tomohiro,Ute, Koichi
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p. 2070 - 2073
(2016/04/26)
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- Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
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2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
- Rajan
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p. 287 - 291
(2015/01/30)
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- SYNTHESIS OF HYDROXYALKYL AMIDES FROM ESTERS
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Hydroxyamides are synthesized from esters. A process of making hydroxyalkyl amides comprises: reacting an ester with a hydroxyalkyl amine having the formula H2N—R3—OH wherein R3 is a substituted or unsubstituted C2 to C5 alkyl, in the presence of a catalyst in an anhydrous solution to form the hydroxyalkyl amides. Monomers suitable for formation of polymeric articles can utilize these hydroxyamides.
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Page/Page column 4
(2012/11/08)
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- Synthesis and evaluation of a photochromic surfactant for organic reactions in aqueous media
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A novel photochromic azobenzene-based surfactant was described for organic chemistry in water. The molecule 4-butylazobenzyl-4′-triazologlucuronic acid sodium salt thus synthesized can be isomerized from its trans to its cis form reversibly in solution by simple light irradiation. That property allowed the recyclability of a model acetylation reaction performed in the surfactant media, compared to the well-known, commercially available sodium dodecyl sulfate surfactant media.
- Drillaud, Nicolas,Banaszak-Léonard, Estelle,Pezron, Isabelle,Len, Christophe
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p. 9553 - 9561
(2013/01/15)
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- Isopropenyl acetate, a remarkable, cheap and acylating agent of amines under solvent- and catalyst-free conditions: A systematic investigation
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Isopropenyl acetate was proved to be an efficient reagent for acetylation of amine in the absence of solvent and catalyst. The corresponding acetamides were obtained in very high yields without any purification.
- Pelagalli, Romina,Chiarotto, Isabella,Feroci, Marta,Vecchio, Stefano
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supporting information; experimental part
p. 2251 - 2255
(2012/09/08)
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- Beckmann rearrangement of oximes using pivaloyl chloride/DMF complex
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A new complex of pivaloyl chloride and DMF was found to be very effective for converting ketoximes into their corresponding amides or lactams with excellent conversion via the Beckmann rearrangement. This method offers significant advantages such as efficiency and mild reaction conditions with shorter reaction time.
- Narahari, Srinivasa Reddy,Reguri, Buchi Reddy,Mukkanti
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experimental part
p. 4888 - 4891
(2011/10/05)
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- Metal acetate/metal oxide in acetic acid: An efficient reagent for the chemoselective N-acetylation of amines under green conditions
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The use of catalytic amount of metal acetate or metal oxide in acetic acid is a new and highly efficient acetylating system for chemoselective N-acetylation of primary and secondary amines in excellent yields under reflux condition. No other solvent is required. The noted features of this method include mild reaction conditions, use of innocuous reagents, excellent yields, convenient work-up, and reuse of catalyst.
- Brahmachari, Goutam,Laskar, Sujay,Sarkar, Sajal
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experimental part
p. 288 - 295
(2010/10/18)
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- A green approach to chemoselective N-acetylation of amines using catalytic amount of zinc acetate in acetic acid under microwave irradiation
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It has been found for the first time that zinc acetate alone can act as a selective A'-acetylating agent without any solvent under closed vessel microwave irradiation. It is also observed that the use of a catalytic amount of this reagent in acetic acid is sufficient enough for smooth running of A'-acetylation of a number of structurally diverse amines, and the reaction is chemoselective with respect to phenols, thiols, acids and alcohols. Herein is reported a simple, efficient, cost-effective and environmentally benign alternative method for chemoselective A'-acetylation of amines using catalytic amount of zinc acetate in acetic acid under microwave irradiation. The reaction procedure requires no other solvent, and is rapid with good to excellent yields.
- Brahmachari,Laskar,Sarkar
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experimental part
p. 1274 - 1281
(2010/12/24)
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- HYDRATE INHIBITORS
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The present invention relates to compounds for controlling gas hydrate formation of the formula (I) and (II) and plugging of gas hydrate forming fluids wherein R1 is selected from the group consisting of H, acetyl and carbonyl derivative; R2 is H, -OR3 or -NR4R5, where: R3 is H, C1-6-alkyl or carbonyl derivative, R4, R5 are selected from the group consisting of H, C1-18-alkyl, alkanol, alkoxy, cyclic/aromatic or alkylene. The invention further comprises compositions and method of producing the compounds of formula (I) and (II), method for controlling gas hydrate formation and plugging of gas hydrate forming fluids, and use of compounds of formula (I) and (II).
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Page/Page column 34-35
(2010/09/18)
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- Transacylation of α-Aryl-β-keto Esters
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The acyl group of an α-aryl-β-keto ester was readily transferred to N-, O-, and S-nucleophiles. The transacylation from arylated diethyl 3-oxoglutarate to amines led to unsymmetrical malonic acid amide esters in high yields. The present reaction proceeded under mild conditions without formation of detectable byproducts. Only simple experimental manipulations were required. This reaction was also found to be sensitive to steric factors, which enabled the chemoselective monoacylation of diamines and amino alcohols without any modifications such as protection.
- Nishiwaki, Nagatoshi,Nishida, Daisei,Ohnishi, Tetsuya,Hidaka, Fumie,Shimizu, Satoru,Tamura, Mina,Hori, Kazushige,Tohda, Yasuo,Ariga, Masahiro
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p. 8650 - 8656
(2007/10/03)
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- Five- and six-membered ring opening of pyroglutamic diketopiperazine
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A variety of ring-opening reactions of pyroglutamic diketopiperazine at both the five-membered and six-membered rings is described. Mild, basic conditions facilitate nucleophilic attack by amines at the diketopiperazine carbonyls giving pyroglutamides in excellent yield. Reaction with nucleophiles under acidic conditions give bis-glutamate derivatives of 2,5-diketopiperazine (DKP). These reactions provide simple, two-step sequences to pyroglutamides and symmetrical diketopiperazines from commercial pyroglutamic acid with control of product dictated by reaction conditions, catalyst, and nucleophile.
- Parrish, Dennis A.,Mathias, Lon J.
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p. 1820 - 1826
(2007/10/03)
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- Platinum catalysed hydrolytic amidation of unactivated nitriles
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The platinum(II) complex, [(Me2PO··H··OPMe2)PtH(PMe2OH)], efficiently catalyses the direct conversion of unactivated nitriles to N- substituted amides with both primary and secondary amines. Possible mechanisms for this reaction are discussed and evidence for initial amidine formation is reported. Isolated yields vary from 51-89%. (C) 2000 Elsevier Science Ltd.
- Cobley, Christopher J.,Van Den Heuvel, Marco,Abbadi, Abdelilah,De Vries, Johannes G.
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p. 2467 - 2470
(2007/10/03)
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- Heterogeneous catalytic conversions with hydrous SnO2
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Hydrous Tin oxide (SnO2) was prepared by the action of conc. HNO3 on tin metal. It was found to catalyse transesterification, amidation and transferhydrogenation in the vapour phase significantly. There was no loss in activity for at least 50 runs of the reactions.
- Waghoo, Gulzar,Jayaram,Joshi
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p. 513 - 520
(2007/10/03)
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- HOBT immobilized on macroporous polystyrene beads: A useful reagent for the synthesis of amides
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Polymer-supported 1-hydroxybenzotriazole (P-HOBT), prepared from macroporous polystyrene beads, was used to synthesize amides from primary and secondary amines.
- Dendrinos, Kleanthis,Jeong, Jeannie,Huang, Wei,Kalivretenos, Aristotle G.
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p. 499 - 500
(2007/10/03)
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- Aminolysis of N-Acylpyrazoles
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1-Acylpyrazoles reacted with amines having a tiny substituted to afford the corresponding amides.The aminolysis with bulky amines was controlled to be retarded by the steric factors.Due to this steric interaction, the stereoselective aminolysis was observed.This selectivity of aminolysis should increase the utility of pyrazoles as auxiliary compounds in the synthetic loop.
- Kashima, Choji,Fukuchi, Iwao,Takahashi, Katsumi,Hosomi, Akira
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p. 1407 - 1412
(2007/10/02)
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- 1,1,1-TRICHLOROPROPANONE: A MILD, SELECTIVE ACETYLATING AGENT
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The use of the title compound in the acetylation of primary and secondary amines is described.
- Salim, Jose Roberto,Nome, Faruk,Rezende, Marcos Caroli
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p. 1181 - 1188
(2007/10/02)
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- REACTIONS OF ESTERS WITH AMINES CATALYSED BY METAL CENTRES
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In the presence of metal catalysts such as AlCl3, SnCl2, FeCl3, CuCl2*2H2O, PhCl3*3H2O, "RuCl3*3H2O" and CuCl, the reaction of the ester RCO2Et (R = Me) with an aliphatic amine R1NH2 (R1 = nPr), at 65 deg C and under a dinitrogen atmosphere gives the corresponding amide, RCONHR1, and ethanol.The catalytic activity increases with increasing acidic nature of the metal centre.Similar results have been obtained with R1 = nBu and R = Me and Et, while no reaction was observed with R1 = Ph.A complex such as Rh(PPh3)3Cl has no catalytic activity in these reactions.From the attempted reaction of CH3CO2Et with nPrNH2 in the presence of Rh(PPh3)3Cl, a yellow complex of formula Rh(PPh3)2(nPrNH2)Cl has been isolated.Its reactivity towards CO, O2, and H2 has been also investigated.
- Porta, Francesca,Pizzotti, Maddalena,Crotti, Corrado,Cenini, Sergio
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p. 475 - 478
(2007/10/02)
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- Incorporation and Deoxygenation of Carbon Dioxide: A Metal-Assisted Facile Conversion of Carbon Dioxide and Primary Amines to Isocyanates
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Metal N-alkylcarbamato complexes (M = Na, n = 1; M = Mn, Co, n =2) were prepared by treating CO2 with a primary amine RNH2 (R = Ph, Cy, Pr) and various complex precursors.For M = Mn or Co and R = Cy, MCl2 can be used as starting material.These complexes were readily decomposed by acyl halides R'COCl (R' = Ph, Me), and two reaction pathways were observed.One led to decarboxylation and formation of amides RNHC(O)R', while the other afforded isocyanate RNCO and carboxylic acid (M = Na) or carboxylic anhydride (M = Mn, Co).Analysis of the reaction products showed that the metal plays a major role in the formation of the isocyanate, intercepting one of the reaction products.A mechanistic rationalization is proposed.
- Belforte, Antonio,Dell'Amico, Daniela Belli,Calderazzo, Fausto
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p. 1891 - 1898
(2007/10/02)
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- Ruthenium Tetroxide Oxidation of N-Acylated Alkylamines: A New General Synthesis of Imides
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Oxidation of various N-acylalkylamines with ruthenium tetroxide (RuO4) was systematically investigated.N-acylalkylamines having an electron-donating group at the α- or β-position with respect to amide nitrogen or an electron-donating alkyl function in the acyl group were smoothly oxidized to the corresponding imides in excellent yields.On the other hand, N-acylalkylamines having an electron-withdrawing group were not oxidized at all, and most of the starting material was recovered.It appears that the reactivity of N-acylalkylamines is closely correlated with the acidity of the carboxylic acid from which the N-acyl group is derived, and also with the electron density at the methylene moiety adjacent to the amide nitrogen atom.Keywords---oxidation; ruthenium tetroxide oxidation; imide synthesis; acyclic imide; amide; ruthenium tetroxide; substituent effect
- Tanaka, Ken-Ichi,Yoshifuji, Shigeyuki,Nitta, Yoshihiro
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p. 364 - 369
(2007/10/02)
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- REACTIONS OF DIETHYL CARBONATE WITH AMINES CATALYZED BY METAL CENTRES
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In the presence of several metal compounds as catalysts such as AlCl3, SnCl2, ZnCl2, Zn(O2CCH3)2*2H2O, FeCl3, "RuCl3*3H2O", RhCl3*3H2O, Rh(PPh3)3Cl, and Ru(PPh3)3Cl2, the reaction of diethyl carbonate, (C2H5O)2CO, with 1-propylamine at 60 deg C and under a dinitrogen atmosphere gives the corresponding carbamate, CH3(CH2)2NHCO2C2H5.The catalytic activity increases by increasing the acidic nature of the metal centre.Compounds such as FeCl3 and AlCl3 were found inactive when the reaction was carried out with aniline instead of 1-propylamine.Preliminary results have shown that FeCl3 is also active as catalyst in the reaction of CH3CO2C2H5 with 1-propylamine to give the corresponding amide CH3CONH(CH2)2CH3.
- Porta, Francesca,Cenini, Sergio,Pizzotti, Maddalena,Crotti, Corrado
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p. 275 - 278
(2007/10/02)
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- Platinum Complex Catalyzed Reductive N-Acylation of Nitro Compounds
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Aromatic and aliphatic nitro compounds reacted with carboxylic acids at 180 deg C for 4 h in the presence of a catalytic amount of PtCl2(PPh3)2 combined with tin(IV) chloride under 60 atm of carbon monoxide pressure to give corresponding N-substituted amides in moderate to fairly good yields.From nitrobenzene, acetanilide was obtained in 91 percent yield.Tin(IV) chloride can be substituted by other Lewis acids such as SnCl2, FeCl3, VCl3, AlCl3, and ZnCl2.The reaction appears to include the formation of nitrene and isocyanate as key intermediates.
- Watanabe, Yoshihisa,Tsuji, Yasushi,Kondo, Teruyuki,Takeuchi, Ryo
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p. 4451 - 4455
(2007/10/02)
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- Solute-Solute Interactions in Non-aqueous Solvents. Enthalpic Interaction Coefficients of Substituted Acetamides Dissolved in N,N-Dimethylformamide
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Enthalpies of dilution of acetamide, N-methylacetamide, N-ethylacetamide, N-propylacetamide, N-butylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide and N,N-dibutylacetamide dissolved in N,N-dimethyacetamide as solvent have been measured calorimetrically at 25 deg C.The results are interpreted in terms of McMillan-Mayer theory.The enthalpic interaction parameters are obtained for pairs, triplets and some quadruplets of solute molecules.All enthalpic pair interaction coefficients but one in this nonaqueous solvent are negative, whereas the triplet coefficients are positive.The concept of "solvophobic interaction" can be used to explain these results in connection with the assumption of the formation of solute-solvent associates.The enthalpic pair interaction coefficients can be described by the additivity approach of Savage and Wood.
- Bloemendal, M.,Somsen, G.
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- OXIDATION-REDUCTION MECHANISMS - INNER-SPHERE AND OUTER-SPHERE ELECTRON TRANSFER IN THE REDUCTION OF IRON(III), RUTHENIUM(III), AND OSMIUM(III) COMPLEXES BY ALKYL RADICALS. MECHANISMS -
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Alkyl radicals are readily oxidized by the tris(phenanthroline) and tris(bipyridine) complexes ML//3**3** plus of iron(III), ruthenium(III), and osmium(III) in acetonitrile solution, the second-order rate constants easily exceeding 10**6 M** minus **1s** minus **1 at 25 degree C. Two oxidative processes are identified as (a) ligand substitution on the coordinated 1,10-phenanthroline to yield various alkylphenanthrolines and (b) cation formation to afford alkenes and N-alkylacetamides (after hydrolysis). Cation formation is characterized by extensive skeletal rearrangement of neopentyl, isobutyl, and n-propyl groups, whereas ligand substitution by the same alkyl radicals occurs without any rearrangement.
- Rollick,Kochi
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p. 1319 - 1330
(2007/10/02)
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- The Effect of Electrochemically Generated Positive Bromine Species in Acetonitrile on the Cleavage of C-Br and C-Cl Bonds.
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The fate of bromine formed from C-Br cleavage during the course of anodic oxidation of alkyl bromides in acetonitrile on platinum has been investigated potentiostatically.It is suggested that positive bromine species are formed and they are potentially reactive towards alkyl bromides, yielding similar products to those obtained by direct anodic oxidation of the same bromides.Furthermore, whereas alkyl chlorides do not undergo C-Cl fission by direct anodic oxidation it is shown that positive bromine species are energetically sufficient to break C-Cl bonds, although not very efficiently.We suggest that a possible structure for the complex between acetonitrile and positive bromine species is mainly +Br3- and the mechanism for its formation is discussed.The spectrum of this species found identical to that of Br3- (269 nm) in acetonitrile.
- Becker, James Y.,Zemach, Dvora
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p. 336 - 340
(2007/10/02)
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