- METHODS OF FORMING IMINES, IMINE-RELATED AND IMINE-DERIVED COMPOUNDS USING GREEN SOLVENTS
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The present disclosure relates to using green solvents to synthesize an array of imines, imine-related and imine-derived compounds in an efficient and eco-friendly matter, satisfying green chemistry requirements. Reaction embodiments are performed using solvents, such as ethyl lactate and dimethyl isosorbide, which are both individually characterized as green. In embodiments, solvents include lactic whey and/or water as co-solvents. In these green solvents, the synthesis process discussed herein can produce up to quantitative yields of product at room temperature in a short duration. Embodiments include a method of forming an imine, imine-related or imine-derived compound product. In embodiments, the methods include mixing an aldehyde reactant with a nucleophilic/nitrogen-containing reactant in a green solvent at a temperature between negative twenty degrees Celsius (?20° C.) and positive fifty degrees Celsius (50° C.); stirring the mixture; and forming an imine, imine-related or imine-derived compound product.
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Paragraph 0190-0193
(2021/10/22)
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- Ruthenium(ii)-catalysed 1,2-selective hydroboration of aldazines
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Herein, an efficient and simple catalytic method for the selective and partial reduction of aldazines using ruthenium catalyst [Ru(p-cymene)Cl2]2 (1) has been accomplished. Under mild conditions, aldazines undergo the addition of pinacolborane in the presence of a ruthenium catalyst, which delivered N-boryl-N-benzyl hydrazone products. Notably, the reaction is highly selective, and results in exclusive mono-hydroboration and desymmetrization of symmetrical aldazines. Mechanistic studies indicate the involvement of in situ formed intermediate [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] (1a) in this selective hydroboration.
- Gunanathan, Chidambaram,Pradhan, Subham,Thiyagarajan, Subramanian
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supporting information
p. 7147 - 7151
(2021/08/30)
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- Binuclear furanyl-azine metal complexes encapsulated in NaY zeolite as efficiently heterogeneous catalysts for phenol hydroxylation
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Two different methods A and B were used for preparing binuclear furanyl-azine metal complexes encapsulated in NaY zeolite. These new heterogeneous catalysts based on Fe(II) or Cu(II) complexes with a metal/ligand molar ratio of 2:1, were characterized by different spectroscopic techniques and chemical analysis which confirm the presence of the metal complexes inside the supercages of the zeolite. M?ssbauer spectroscopy technique analysis confirms the presence of the Fe3+- complexes in octahedral coordination. The new heterogeneous catalysts were catalytic evaluated by phenol hydroxylation and compared with the encapsulated metal furanyl-azine complexes in NaY zeolite. The zeolite themselves do not present any activity and the presence of the metal complexes improve their activity. All heterogeneous catalysts enhance higher conversion of phenol to catechol.
- Ku?niarska-Biernacka,Raposo,Batista,Soares,Pereira,Parpot,Oliveira,Skiba,Jartych,Fonseca,Neves
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- Selective Reduction of Azines to Benzyl Hydrazones with Sodium Borohydride Catalyzed by Mesoporous Silica-Supported Silver Nanoparticles: A Catalytic Route towards Pyrazole Synthesis
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The catalytic activity of supported silver nanoparticles on mesoporous silica was studied, for the selective reduction of azines into benzyl hydrazones using sodium borohydride as mild reducing agent. Different sizes of silver nanoparticles supported on mesoporous silica (Ag/HMS) were successfully prepared by two methods, i.e., wet impregnation followed by reduction with hydrogen at 350 °C and in situ deposition/reduction with a mixture of amines (ethanolamine and ethylenediamine). The Ag/HMS (amines) catalyst was found to promote the selective 1,2-reduction of aryl-substituted azines, compared to the corresponding 1,4-reduction that occurs in general reduction processes. This catalytic transfer hydrogenation process found to be clean, fast and quantitative (>99% yields and selectivity) towards benzyl hydrazone synthesis under mild conditions. Of great importance is that under the present catalytic conditions reducible functional groups remain intact. Formal kinetics, support the in situ formation of silver hydride species being responsible for the reduction process. The presence of protic polar methanol enhanced the catalytic activity of Ag/HMS. Based on the recycling studies the catalytic system Ag/HMS-NaBH4 was found to catalyze the selective reduction of azines nine times without significant loss of its activity. Finally, a one-pot reaction between the in situ produced benzyl hydrazones and a series of nitrostyrenes readily provided the regioselective synthesis of 1,3,5-subtituted pyrazoles, highlighting a useful synthetic application of the catalytic protocol. (Figure presented.).
- Charistoudi, Evangelia,Kallitsakis, Michael G.,Charisteidis, Ioannis,Triantafyllidis, Kostas S.,Lykakis, Ioannis N.
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supporting information
p. 2949 - 2960
(2017/09/08)
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- A Copper-Benzotriazole-Based Coordination Polymer Catalyzes the Efficient One-Pot Synthesis of (N′-Substituted)-hydrazo-4-aryl-1,4-dihydropyridines from Azines
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A series of new (N′-substituted)-hydrazo-4-aryl-1,4-dihydropyridines was successfully synthesized via a facile one-pot catalytic pathway utilizing azines and propiolate esters as starting materials and a one-dimensional copper benzotriazole-based coordination polymer as catalyst. In the absence of catalyst, the corresponding 5-substituted 4,5-dihydropyrazoles were formed in moderate to high yields. Fine-tuning of the catalysts allowed us to gain more insights regarding the plausible reaction mechanism. (Figure presented.).
- Kallitsakis, Michael,Loukopoulos, Edward,Abdul-Sada, Alaa,Tizzard, Graham J.,Coles, Simon J.,Kostakis, George E.,Lykakis, Ioannis N.
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supporting information
p. 138 - 145
(2017/01/14)
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- Synthesis and evaluation of certain symmetrical schiff bases as inhibitors of MDA-MB-241 human breast cancer cell proliferation
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A series of symmetrical Schiff base derivatives (L1-L7) were designed by a one-pot condensation reaction of various aldehyde/ketone compounds with hydrazine under mild conditions (room temperature, 3 days), using ether as solvent and acetic acid as catalyst. The target products were characterized and analysed by 1H and 13C NMR, FT-IR and liquid chromatography mass spectrometry (LC/MS). Our research focuses on the identification of synthetically chemotherapeutic substances able to inhibit, delay, or reverse the process of carcinogenesis in several stages. The target compounds presenting two regions for SAR evaluation were screened for their activity toward MDA-MB-241 breast cancer cell proliferation for the first time. Compound (1E, 2E)-1,2-bis(1-(3-nitrophenyl)ethylidene) hydrazine (L6) showed significant inhibitory activity (IC50 = 7.08 μg/mL).
- Radi, Smaail,Tighadouini, Said,Feron, Olivier,Riant, Olivier,Mabkhot, Yahia N.
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p. 205 - 209
(2016/03/15)
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- An expeditious synthetic approach towards the synthesis of Bis-Schiff bases (aldazines) using ultrasound
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Aldazines (Bis-Schiff bases) 1-24 were synthesized using aromatic aldehydes (heterocyclic and benzaldehydes) and hydrazine hydrate under reflux using conventional heating and/or via ultrasound irradiation using BiCl3 as catalyst. Ultrasonication conditions with cat. BiCl3 proved to be an effective, environmentally friendly synthetic procedure. This methodology is robust in the presence of electron donating and electron withdrawing groups affording desired products with high yields (>95%) in just a couple of minutes vs. hours using conventional heating.
- Khan, Khalid M.,Jamil, Waqas,Ambreen, Nida,Taha, Muhammad,Perveen, Shahnaz,Morales, Guillermo A.
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p. 1200 - 1205
(2014/02/14)
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- Rapid, chemoselective and facile synthesis of azines by hydrazine/I2
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We report the reaction of hydrazine hydrate with carbonyl compounds in the presence of molecular iodine at 0-10°C, which affords symmetrical azines in excellent yields in 1 to 4 min without any adverse effect on other substituents. The reactions are rapid and chemoselective, afford excellent yields, and have high-purity products. The workup procedure is environmentally benign and does not require solvent extraction. Copyright Taylor & Francis Group, LLC.
- Nanjundaswamy,Pasha
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p. 3417 - 3420
(2008/02/13)
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- Selective protection of carbonyl compounds as azines and their facile regeneration
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Carbonyl compounds with freshly prepared hydrazinium formate successfully yielded the corresponding azines in excellent yields. In turn, azines were deprotected to the corresponding carbonyls using triethylammonium chlorochromate chemoselectively. Copyright Taylor & Francis Group, LLC.
- Nanjundaswamy,Pasha
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p. 3161 - 3165
(2007/10/03)
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- Synthesis of N-imino-β-lactams from 2,3-diaza-1,3-dienes (azines) mediated by POCl3
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Symmetrically substituted azines derived from aromatic aldehydes have been found compatible with the reaction of phenoxyacetic acid activated by POCl 3. N-Imino-β-lactams are efficiently obtained by this method in good to excellent yields with varying levels of cis, trans-selectivity.
- Sharma,Anand,Kaur, Gurpreet
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p. 1273 - 1275
(2008/09/21)
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- 2,3-Diaza-1,3-dienes (azines) as substrates for the Staudinger reaction. Synthesis and reactivity of N-imino-β-lactams
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The reaction of aromatic and aliphatic azines with different ketene precursors, such as the acid chloride/Et3N system, alkoxychromium(0) carbenes, and free diphenyl ketene, gives N-imino-β-lactams in good to excellent yields, with good levels of cis,trans-selectivity. A wide variety of symmetrically-substituted azines derived from aldehydes and ketones are compatible with the Staudinger reaction. Chiral N-imino-β-lactams derived from symmetrically or unsymmetrically (mixed) chiral azines are also obtained in good yields as essentially single enantiomers (de > 95%). Different reaction intermediates, including hemiaminals, oxadiazols, and hydrazides have been isolated. Free diphenyl ketene forms Diels-Alder adducts and N-acylazadienes in addition to the previously reported N-imino-β-lactams. The usual reactivity of the β-lactam ring is modified in N-imino-β-lactams by the presence of the imino group. Thus, β-hydrazonoesters, N-alkylamino-β-lactams, and NH-β-lactams can be efficiently obtained by base-catalyzed 2-azetidinone ring opening, catalytic hydrogenation, and ozonolysis, respectively.
- Alcaide,Miranda,Perez-Castells,Polanco,Sierra
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p. 8003 - 8010
(2007/10/02)
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- Oxidative Transformations of Aldazines and Ketazines with Organic Peroxyacids
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Oxidation of aromatic aldazines and ketazines with various peroxycarboxylic acids was investigated.It was found that one part of azine molecule 2 was converted into carbonyl compound 1 or related acid 3 while the second part was transformed into carboxylic ester 4 related to peroxyacid used as an oxidant.It was revealed that aromatic azines could be used as a source of diazaarylmethanes and mechanisms of reactions studied were postulated. aldazines, carboxylic esters, ketazines, oxidation, peroxycarboxylic acids
- Mlochowski, J.,Giurg, M.
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p. 2333 - 2342
(2007/10/02)
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- CHLOROSULFONATION OF DIARYL AZINES
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Benzaldehyde- and o-, m-, p-anisaldehyde azines; thiophene-2-carboxaldehyde, and biphenyl-4-carboxaldehyde azines (1-8) reacted with excess chlorosulfonic acid to give the disulphonyl chlorides (1a-8a).These were condensed with amines and hydrazine to give 27 derivatives, (Table I) for biocidal evaluation.The orientation of sulfonation is discussed in relation to the stereoelectronic factors and the spectral data.Attempted chlorosulfonation of furan-2-carboxaldehyde azine (9) gave an impure product which could not be clearly characterized as the morpholidate derivative.
- Cremlyn, Richard J.,Swinbourne, Frederick J.,Graham, Stephen,Cavaleiro, Jose A. S.,Domingues, Fernando J.,Dias, Maribel
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- ON THE MULTIPLICITY OF CARBENES CONJUGATED WITH PYRROLE AND FURAN MOIETIES: MOLECULAR ORBITAL CALCULATION AND REACTION OF 2-(1-METHYL)PYRROLYLMETHYLENE AND 2-FURYLMETHYLENE WITH CIS- AND TRANS-STILBENES
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The reaction of 2-(1-methyl)pyrrolylmethylene and 2-furylmethylene with cis- and trans-stilbenes proceeded in a stereospecific manner to give the corresponding cyclopropane derivatives to show that the multiplicities of these carbenes are singlet.The molecular orbital calculation showed that these carbenes are triplet in their ground state and nucleophilic both in singlet and triplet states.
- Saito, Katsuhiro,Ushida, Takahiro,Fushihara, Hiroshi,Yamashita, Yoshiro,Tanaka, Shoji,Takahashi, Kensuke
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p. 115 - 122
(2007/10/02)
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- THERMOLYSIS OF SODIUM SALTS OF TOSYLHYDRAZONES OF SOME HETEROCYCLIC ALDEHYDES IN THE PRESENCE OF SILVER CHROMATE: 1,3 NC MIGRATION OF TOSYL GROUP
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The thermal decompositions of sodium salts of tosylhydrazones of furfural, thiophene-2-aldehyde, 1-methylpyrrole-2-aldehyde, and pyridine-2-aldehyde in the presence of silver chromate gave 2-furyl(p-toluenesulfonyl)methane, thiophene-2-(p-toluenesulfonyl)methane, 1-methylpyrrole-2-(p-toluenesulfonyl)methane, and pyridine-2-(p-toluenesulfonyl)methane, respectively, via 1,3 NC migration of tosyl group.The same type of reactions with sodium salts of tosylhydrazones of thiophene-3-aldehyde, pyridine-3-aldehyde, and pyridine-4-aldehyde also afforded the corresponding p-toluenesulfonylmethanes but the yields were slightly lower comparing to the above cases.
- Saito, Katsuhiro,Ishihara, Hiraku
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p. 1891 - 1898
(2007/10/02)
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- Synthesis and X-ray Photoelectron Spectra of Some Azines
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Arylhydrazone-N-carboxylic esters (I) were treated with hydrazine hydrate, or sodium hydroxide, to give the hydrazones (II).Acidification of the latter produced the corresponding azines (III).The structures of compounds I - III were substantiated by chemical and spectral analysis.
- El-Rayyes, Nizar R.,Katrib, Ali H.
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p. 132 - 134
(2007/10/02)
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- The Heteroaromatic Cope Rearrangement of 1-Pyridyl-, 1-Furyl-, and 1-Thienyl-2-vinylcyclopropanes
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The 1-pyridyl-2-vinylcyclopropanes 3a and 5a rearrange to the cycloheptapyridines 10a and b on heating in an aromatic solvent.The reaction may be considered as an aromatic Cope rearrangement to 9, followed by a rearomatization step.N-Methylation of the starting vinylcyclopropane lowers the necessary reaction temperature markedly.The primary products 19 and 20 of the Cope rearrangement of the 1-furyl- or 1-thienyl-2-vinylcyclopropanes 3, 5c, d are thermally stable under the reaction conditions.The rearomatization of 19 and 20 is catalyzed by electrophiles (H+, CH3I) and, to a lower extent, by bases (pyridine).On heating to about 200 deg C in an inert aromatic solvent, 19a undergoes Retro-Cope rearrangement to 3c, aromatization to 21 as well as rearrangement to the cyclopentene 23.In all cases, the (Z)-vinylcyclopropanes undergo the Cope rearrangement faster than their (E)-isomers.
- Maas, Gerhard,Hummel, Christine
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p. 3679 - 3696
(2007/10/02)
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