- Aerobic oxidation of primary amines to amides catalyzed by an annulated mesoionic carbene (MIC) stabilized Ru complex
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Catalytic aerobic oxidation of primary amines to the amides, using the precatalyst [Ru(COD)(L1)Br2] (1) bearing an annulated π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand L1, is disclosed. This catalytic protocol is distinguished by its high activity and selectivity, wide substrate scope and modest reaction conditions. A variety of primary amines, RCH2NH2 (R = aliphatic, aromatic and heteroaromatic), are converted to the corresponding amides using ambient air as an oxidant in the presence of a sub-stoichiometric amount of KOtBu in tBuOH. A set of control experiments, Hammett relationships, kinetic studies and DFT calculations are undertaken to divulge mechanistic details of the amine oxidation using 1. The catalytic reaction involves abstraction of two amine protons and two benzylic hydrogen atoms of the metal-bound primary amine by the oxo and hydroxo ligands, respectively. A β-hydride transfer step for the benzylic C-H bond cleavage is not supported by Hammett studies. The nitrile generated by the catalytic oxidation undergoes hydration to afford the amide as the final product. This journal is
- Yadav, Suman,Reshi, Noor U Din,Pal, Saikat,Bera, Jitendra K.
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p. 7018 - 7028
(2021/11/17)
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- Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
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The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
- Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
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p. 3115 - 3125
(2019/04/26)
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- A Convenient Protocol for the Synthesis of Fatty Acid Amides
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Several classes of biologically occurring fatty acid amides have been reported from mammalian and plant sources. Many amides conjugated with fatty acids of mammalian origin exhibit specific activation of individual receptors. Their potential as pharmacological tools or as lead compounds towards the development of novel therapeutics is of great interest. Hence, access to such amides by a practical, high-yielding and scalable protocol without affecting the geometry or position of sensitive functionalities is needed. A protocol that meets all these requirements involves activation of the corresponding acid with carbonyl diimidazole (CDI) followed by reaction with the desired amine or its hydrochloride. More than fifty compounds have been prepared in generally high yields.
- Johansson, Silje J. R.,Johannessen, Tonje,Ellefsen, Christiane F.,Ristun, Mali S.,Antonsen, Simen,Hansen, Trond V.,Stenstrom, Yngve,Nolsoe, Jens M. J.
-
supporting information
p. 213 - 217
(2019/01/14)
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- Metal-Free Thermal Activation of Molecular Oxygen Enabled Direct α-CH2-Oxygenation of Free Amines
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Direct oxidation of α-CH2 group of free amines is hard to achieve due to the higher reactivity of amine moiety. Therefore, oxidation of amines involves the use of sophisticated metallic reagents/catalyst in the presence or absence of hazardous oxidants under sensitive reaction conditions. A novel method for direct C-H oxygenation of aliphatic amines through a metal-free activation of molecular oxygen has been developed. Both activated and unactivated free amines were oxygenated efficiently to provide a wide variety of amides (primary, secondary) and lactams under operationally simple conditions without the aid of metallic reagents and toxic oxidants. The method has been applied to the synthesis of highly functionalized amide-containing medicinal drugs, such as O-Me-alibendol and -buclosamide.
- Ghosh, Santanu,Jana, Chandan K.
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p. 260 - 266
(2018/02/19)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0138; 0139; 0140; 0141; 0142
(2018/05/07)
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- METHOD FOR PRODUCING FATTY ACID AMIDES
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PROBLEM TO BE SOLVED: To provide a method for producing fatty acid amides, suitable for continuous production at high reaction rate. SOLUTION: There is provided a method for producing fatty acid amides including the steps of: supplying a fatty acid into a reactor and subjecting the supplied fatty acid to desulfurization treatment by a desulfurizer in the reactor; supplying ammonia into the reactor and reacting the fatty acid subjected to desulfurization treatment with the supplied ammonia in the presence of an amidation catalyst to obtain a fatty acid amide; and leading unreacted ammonia and water vapor out from the reactor and separating ammonia and water by distillation and supplying the separated ammonia into the reactor via a supply port of ammonia. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2018,JPO&INPIT
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Paragraph 0046-0049
(2018/10/10)
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- Method and apparatus for manufacturing carboxylic acid amide compound
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The present invention relates to a process and an apparatus for producing a carboxylic acid amide compound, and more particularly, to a process for producing a carboxylic acid amide compound which alternately performs a reaction process of a first manufacturing process that promotes the reaction between a first carboxylic acid and a first ammonia in the presence of a first catalyst and a reaction process of a second manufacturing process that promotes the reaction between a second carboxylic acid and a first ammonia in the presence of a second catalyst wherein each of them is progressed alternately between each preparation process so that the reaction between the carboxylic acid and the ammonia, which is intermittently carried out by the respective preparation processes, can be continuously performed, and moreover, the time required for the respective preparation processes is shortened, so that the carboxylic acid amide compound can be produced in a large amount in a short time.
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Paragraph 0059-0061; 0068
(2017/06/02)
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- NOVEL LIPIDS AND LIPID NANOPARTICLE FORMULATIONS FOR DELIVERY OF NUCLEIC ACIDS
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Compounds are provided having the following structure: (I) or a pharmaceutically acceptable salt, tautomer or stereoisomer thereof, wherein R1a, R1b, R2a, R2b, R3a, R3b, R4a, R4b, R5, R6, R7, R8, R9, L1, L2, a, b, c, d and e are as defined herein. Use of the compounds as a component of lipid nanoparticle formulations for delivery of a therapeutic agent, compositions comprising the compounds and methods for their use and preparation are also provided.
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Page/Page column 75
(2016/05/02)
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- N4-Acyl derivatives as lipophilic prodrugs of cidofovir and its 5-azacytosine analogue, (S)-HPMP-5-azaC: Chemistry and antiviral activity
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Even number fatty acid residues - docosanoyl (behenoyl) and stearoyl were selected for introduction to the N4-position of (S)-1-[3-hydroxy-2- (phosphonomethoxy)propyl]cytosine) (HPMPC, cidofovir), and its 5-azacytosine counterpart, (S)-1-[3-hydroxy-2-(phosphonomethoxy)propyl]cytosine) (HPMP-5-azaC) with the aim to prepare a new type of lipophilic prodrugs. The study on the influence of these modifications to the stability and biological activity of both antivirals was performed. Different reactivity of both systems towards acylation reactions was also found: the 4-NH2 group of cidofovir was more reactive compared to that of HPMP-5-azaC. In 5-azacytosine derivatives, we found mostly a destabilizing effect of the N4-acylation but this could be compensated by a positive influence of the esterification of the phosphonate group. Chemical stability of the 5-azacytosine moiety in the HPMP series is increasing in the following order: HPMP-5-azaC 4-behenoyl derivative of the hexadecyloxyethyl ester of cyclic HPMP-5-azaC. The free phosphonic acid (N4-behenoyl-HPMPC) appeared to be a more potent and selective inhibitor of herpesvirus replication than the parent HPMPC derivative.
- Kre?merová, Marcela,Pohl, Radek,Masojídková, Milena,Balzarini, Jan,Snoeck, Robert,Andrei, Graciela
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p. 2896 - 2906
(2014/05/06)
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- LOW MOLECULAR WEIGHT GELATORS FOR CRUDE OIL, PETROLEUM PRODUCT OR CHEMICAL SPILL CONTAINMENT
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Low molecular weight gelators, methods of making such gelators, organogels comprising such gelators and systems and methods of using such gelators for the containment and/or remediation of a release and/or spill of a crude oil, a petroleum product and/or a chemical is described. In exemplary systems and methods, gels and/or emulsions formed from the combination and/or contact of such gelators and at least one of a crude oil, a petroleum product and a chemical from a release and/or spill into the environment can be used to recover these oils or chemicals while allowing the gelators to be recovered and reused to clean up or contain additional crude oil, petroleum products or chemicals.
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Page/Page column 47
(2012/04/23)
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- Electrospray ionization and collision induced dissociation mass spectrometry of primary fatty acid amides
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Primary fatty acid amides are a group of bioactive lipids that have been linked with a variety of biological processes such as sleep regulation and modulation of monoaminergic systems. As novel forms of these molecules continue to be discovered, more emphasis will be placed on selective, trace detection. Currently, there is no published experimental determination of collision induced dissociation of PFAMs. A select group of PFAM standards, 12 to 22 length carbon chains, were directly infused into an electrospray ionization source Quadrupole Time of Flight Mass Spectrometer. All standards were monitored in positive mode using the [M + H]+ peak. Mass Hunter Qualitative Analysis software was used to calculate empirical formulas of the product ions. All PFAMs showed losses of 14 m/z indicative of an acyl chain, while the monounsaturated group displayed neutral losses corresponding to H2O and NH3. The resulting spectra were used to propose fragmentation mechanisms. Isotopically labeled PFAMs were used to validate the proposed mechanisms. Patterns of saturated versus unsaturated standards were distinctive, allowing for simple differentiation. This determination will allow for fast, qualitative identification of PFAMs. Additionally, it will provide a method development tool for selection of unique product ions when analyzed in multiple reaction monitoring mode.
- Divito, Erin B.,Davic, Andrew P.,Johnson, Mitchell E.,Cascio, Michael
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experimental part
p. 2388 - 2394
(2012/07/27)
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- An improved method for the conversion of nitriles to amides using N,N-disubstituted hydroxylamine
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An improved method for the selective hydration of nitriles to amides employing N,N-disubstituted hydroxylamine is described leading to a reduction in reaction time and improved yield. Amides having electron-donating groups, which were not reported using the original method, were obtained in excellent yields. The amount of N,N-disubstituted hydroxylamine was reduced from three equivalents to one equivalent and the use of water as the reaction medium is environmentally friendly.
- Ma, Xiao-Yun,Lu, Ming
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experimental part
p. 480 - 483
(2011/10/18)
-
- Lizard epidermal gland secretions. II. Chemical characterization of the generation gland secretion of the sungazer, cordylus giganteus
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In lizards, the epidermal glands of the femoral and precloacal regions are involved in the production of semiochemicals. In addition to its femoral glands, the giant girdled lizard, or sungazer, Cordylus giganteus, which is endemic to South Africa, has generation glands as an additional potential source of semiochemicals. These epidermal glands are described as glandular scales that overlay the femoral glands and are included in the normal epidermal profile located in the femoral (thigh) and anterior antebrachial (fore-leg) regions of the male sungazer. GC-MS analysis of the generation gland secretions and the trimethylsilyl derivatives of some of the steroidal constituents was employed to identify 59 constituents, including alkenes, carboxylic acids, alcohols, ketones, aldehydes, esters, amides, nitriles, and steroids. The quantitative differences of the volatile constituents of the fore- and hind-leg generation glands were compared between individuals. This is the first report on the chemical composition of generation glandular material of lizards.
- Louw, Stefan,Burger, Ben V.,Le Roux, Maritha,Van Wyk, Johannes H.
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supporting information; experimental part
p. 1364 - 1369
(2011/08/09)
-
- FAST RECOVERY OF THIXOTROPY BY ORGANOGELS WITH LOW MOLECULAR WEIGHT GELATORS
-
Low molecular weight gelators, methods of making such gelators, organogels comprising such gelators and methods of using such organogels are described. In exemplary methods, the gelators can be used in a variety of applications including the delivery of pharmaceutical active pharmaceutical ingredients, in food, cosmetics and consumer products, and in containing the unexpected release of chemical that occur for example in spills.
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- Sensitized photolysis of stearic acid azide
-
In an IR-spectroscopic study of the sensitized photolysis of stearic acid azide in a solution of benzene, it was found that the introduction of Michler's ketone into the system decreased the efficiency of isocyanate formation by a factor of about 10. It was hypothesized that the azide photolysis in the presence of Michler's ketone can be explained by the formation of a complex of the acyl azide with the ketone in a triplet excited state, a displacement of electron density from the acyl azide group, and its degradation with the formation of a triplet acylnitrene, which is incapable of rearranging into isocyanate.
- Budruev,Oleinik
-
experimental part
p. 521 - 524
(2012/05/04)
-
- Vernonia oil: Conversion to a mixture of tertiary amines including N,N-Dimethyl-(12S,13R)-Epoxy-cis-9-Octadecenyl amine
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Vernonia galamensis is a new potential industrial oilseed crop found in tropical Africa. It is the source of a naturally epoxidized oil called vernonia oil (VO) which is extracted from the seed of the plant. In this study VO was used as the starting material for the synthesis of a mixture of amines, with the major product amine being N,N-dimethyl-(12S,13R)-epoxy-cis-9-octadecenyl amine. VO was transesterified via a base catalyzed methanolysis using sodium methoxide to yield VO methyl esters (VOME). Aminolysis of the VOME with dimethylamine as reagent and solvent under reflux conditions afforded the tertiary amides, with N,N- dimethyl-(12S,13R)-epoxy-cis-9-octadecenyl amide as the major product. The mixture was then subjected to metal hydride reduction with lithium aluminum hydride in diethylether under reflux conditions to obtain the desired amine mixture including N,N-dimethyl-(12S,13R)-epoxy-cis-9-octadecenyl amine. Electron impact mass spectrometry was used to characterize the mixture of amines. Additionally, proton NMR, 13C NMR, and FTIR were used for characterization of N,N-dimethyl-(12S,13R)-epoxy-cis-9-octadecenyl amine. To further confirm the conversion of VO to the amines, the quaternary ammonium salts were synthesized and characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.
- Johnson, Nikki S.,Ayorinde, Folahan O.
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experimental part
p. 1425 - 1430
(2011/11/11)
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- Selective hydrolysis of nitriles to amides using NaOH-PEG under microwave irradiation
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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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- Reduction of Azides with Zinc Borohydride
-
Zinc borohydride in 1,2-dimethoxyethane provides an efficient procedure for the reduction of organic azides.Aroyl, acyl, and arylsulfonyl azides readily undergo reduction at room temperatue to produce amides and sulfonamides in excellent yields; however, substitution with electron-withdrawing groups in the aroyl azides leads to the corresponding benzyl alcohols.Reduction of aryl and alkyl azides has also been achieved in high yields, under some modified conditions.
- Ranu, Brindaban C.,Sarkar, Arunkanti,Chakraborty, Rupak
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p. 4114 - 4116
(2007/10/02)
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- A New Method for the Synthesis of Amides from Amines: Ruthenium Tetroxide Oxidation of N-Protected Alkylamines
-
A simple synthetic method for the preparation of amides from the corresponding primary alkylamines was elaborated using ruthenium tetroxide (RuO4) oxidation as a key step.
- Tanaka, Ken-Ichi,Yoshifuji, Shigeyuki,Nitta, Yoshihiro
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p. 3125 - 3129
(2007/10/02)
-
- Thermal, Dielectric and Polarized Microscopy Studies of 1-Octadecylamine
-
Measurements of the physical properties of 1-octadecylamine were carried out in a temperature range of 30 to 120 deg C.The melting point of the compound was observed at 55 deg C and no liquid crystalline phase was found within this temperature range.The decomposition point of the carbonate of this amine was found to be a little higher than the melting point.A mixture of the amine with a small amount of its carbonate gave DSC curve similar to that of typical liquid crystalline materials.
- Nakamura, Naotake,Okada, Masao,Okada, Yutaka,Sugita, Kaichiro
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p. 181 - 186
(2007/10/02)
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- Acylated hindered hexahydropyrimidines and their use as light stabilizing agents
-
An acylated, hindered hexahydropyrimidine of the formula STR1 wherein R1, R2, R3 and R4 may be the same or different independently of each other and are alkyl having 1 to 6 carbon atoms, when unsubstituted, or alkyl or aryl substituted; R5 and R6 may be the same or different and are hydrogen, or alkyl; R7 is selected from the group consisting of: alkyl having 1 to 20 carbon atoms, substituted alkyl where the alkyl without substitution has 1 to 20 carbon atoms and where substituents may be up to five lower alkyl groups, arylalkyl, cycloalkyl having 3 to 12 carbon atoms, aryl aryl substituted with 1 to 3 substituents seleted from the group consisting of: lower alkyl, lower alkoxy, and hydroxyl; STR2 wherein R9 is unsubstituted or substituted with alkyl, R10 is hydroxyl, lower alkoxy, phenoxy and the group STR3 and R8 is hydrogen, alkyl, substituted alkyl, arylalkyl, hydroxyl, oxyl and STR4 wherein R11 is unsubstituted or substituted alkyl.
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