An Easy Access to Benzofurans via DBU Induced Condensation Reaction of Active 2-Hydroxy Acetophenones with Phenacyl Chlorides: A Novel Class of Antioxidant Agents

A convenient and efficient one-pot synthesis of benzofurans 3a, 3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, 3j, 3k, 3l, 3m, 3n, 3o, 3p, 3q, 3r, 3s, 3t has been described from 2-hydroxy acetophenones and phenacyl chlorides in the presence of DBU. The procedure was applicable for a variety of phenacyl chlorides and provides a variety of benzofurans with higher yields. DBU acts as a base and as well as nucleophiles. All the derivatives were subjected to in vitro antioxidant screenings against representative 2,2-diphenyl-1-picryl-hydrazyl and 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals and results worth for further investigations.

Microwave mediated reduction of heterocycle and fluorine containing nitroaromatics with Mo(CO)(6) and DBU

Heterocycle containing nitroaromatics were reduced by Mo(CO)(6) and DBU in EtOH under microwave irradiation within 15 min. Under the same conditions, 4-fluoronitrobenzene was reduced to 4-fluoroaniline, whereas 2-chloro-1-fluoro-4-nitrobenzene afforded a mixture of 3-chloro-4-fluoroaniline and 3-chloro-4-ethoxyaniline. The extent of the competing SNAr/reduction process could be influenced by the nature of the solvent, with t-BuOH the inert solvent of choice. The latter was used as solvent for SNAr/reductions of 2-chloro-1-fluoro-4-nitrobenzene with S-nucleophiles to yield 3-chloro-4-mercaptoanilines. Crown Copyright (c) 2008 Published by Elsevier Ltd. All rights reserved.

Molybdenum hexacarbonyl and DBU reduction of nitro compounds under microwave irradiation

An ethanolic mixture of molybdenurn hexacarbonyl and DBU mediates the reduction of nitroarenes to the corresponding anilines in excellent yields in 15-30 minutes under microwave irradiation.

Neighboring group effect: DBU-promoted ring transformation of substituted isoxazoles to substituted pyrroles

A novel DBU-promoted ring transformation of substituted isoxazoles to substituted pyrroles is described

ChemInform Abstract: Synthesis Based on Cyclohexadienes. Part 16. Synthesis of Methyl 2,7-Dimethyltricyclo (5.2.2.01,5)undec-5-ene-6-carboxylates

Synthesis of methyl 2, 7-dimethyltricyclo{5.2.2.0(1,5}undec-5-en-6-carboxylates, the tricyclic skeleton present in (+)-allo-cedrol (1) is described using the Diels-Alder strategy. Thus, Birch reduction of the aromatic acid 8 gives 5, the methyl ester of which is isomerised with DBU to a 1:1 mixture of the dienes 6 and 4. Cycloaddition of this mixture with 2-chloroacrylonitrile followed by hydrolysis yields the ketone 60 having the tricyclo{5.2.2.0(1.5)}undec-5-ene framework. Similar reaction with methyl vinyl ketone affords the regioisomeric adducts 61 and 62.

Synthesis of benzofuran based 1,3,5-substituted pyrazole derivatives: As a new class of potent antioxidants and antimicrobials-A novel accost to amend biocompatibility

In search for a new antioxidant and antimicrobial agent with improved potency, we synthesized a series of benzofuran based 1,3,5-substituted pyrazole analogues (5a-l) in five step reaction. Initially, o-alkyl derivative of salicyaldehyde readily furnish corresponding 2-acetyl benzofuran 2 in good yield, on treatment with 1,8-diaza bicyclo5.4.0]undec-7-ene (DBU) in the presence of molecular sieves. Further, aldol condensation with vanillin, Claisen-Schmidt condensation reaction with hydrazine hydrate followed by coupling of substituted anilines afforded target compounds. The structures of newly synthesized compounds were confirmed by IR, H-1 NMR, C-13 NMR, mass, elemental analysis and further screened for their antioxidant and antimicrobial activities. Among the tested compounds 5d and 5f exhibited good antioxidant property with 50% inhibitory concentration higher than that of reference while compounds 5h and 5l exhibited good antimicrobial activity at concentration 1.0 and 0.5 mg/mL compared with standard, streptomycin and fluconazole respectively. (C) 2012 Elsevier Ltd. All rights reserved.

Modificação química de amostras de poli(metacrilato de metila) comerciais com aminas funcionalizadas assistidas por micro-ondas

Este trabalho avaliou a reação de amidação sob catálise de DBU/NaCN de amostras comerciais de poli(metacrilato de metila), (PMMA), massa molar 60.000 u.m.a. com as aminas, alilamina, 2-morfolilaminoetano, 1-(3-aminopropil)-imidazol e N,N-dimetil-trimetilenodiamina com ativação por reator de micro-ondas. O estudo com alilamina e 2-morfolilaminoetano se mostrou eficaz, apresentando percentuais de derivatização significativos (27% e 37% , respectivamente). A quantidade de material polimérico obtido na purificação foi de cerca de 36 % para as duas aminas. O estudo evidenciou a importância dos catalisadores DBU/NaCN, pois sem eles a reação não ocorre e quando utilizados isoladamente, o grau de incorporação é muito menor. Já o estudo com as aminas 1-(3-aminopropil)-imidazol e N,N-dimetil-trimetilenodiamina mostrou-se ineficaz devido à dificuldade de purificação dos produtos. Tentativas de purificação por precipitação com metanol e soluções hidrometanólicas de diferentes concentrações mostraram-se ineficazes. Os novos PMMA modificados foram caracterizados por FT-IR, RMN-1H e análise elementar. Foram observadas alterações na taticidade do PMMA em reações ativadas por micro-ondas

Amidação de Poli( metacrilato de metila)

Nesta dissertação foram avaliadas metodologias para reação de amidação de amostras comerciais de poli (metilmetacrilato), PMMA, com alilamina e benzilamina. A reação foi executada em tubo selado sob aquecimento a 90 C por sete dias, sem que nenhuma quantidade mensurável de amida pudesse ser detectada por FTIR e RMN. A reação foi reavaliada sob catalise de DBU, 3,4% molar, sem que nenhum resultado positivo obtido. O emprego de DBU associado ao NaCN como co-catalisador mostrou-se eficaz é o PMMA pode ser derivatizado em 30 %, com alilamina, e 13 % com benzilamina, sob as mesmas condições de temperatura e tempo. A analise elementar e o RMN-1H foram conclusivos na quantificação das reações enquanto o FTIR mostrou-se pouco eficaz devido a sobreposições de bandas. A taticidade das amostras comerciais de PMMA e do material produzido pode ser avaliada por RMN. Experimentos exploratórios efetuados em forno de microondas monomodo sob as mesmas relações molares com aquecimento a 120 C por 30 minutos com 80 W de potencia não foram capazes de promover alterações na matriz polimérica

N-arylamides from selenium-catalyzed reactions of nitroaromatics and amides in the presence of carbon monoxide and mixed organic bases

N-Arylamides were exclusively obtained in moderate to good yields from selenium-catalyzed reactions of nitroaromatics with amides in the presence of CO and mixed organic bases Et3N and DBU.

Selenium-catalyzed reductive carbonylation of 2-nitrophenols to 2-benzoxazolones

2-Benzoxazolones or 2-benzimidazolones are synthesized in moderate to good yields in the presence of a base (KOH, NaOH, KOAc, NEt3, DBU) at atmospheric pressure or under a high pressure of CO by one-pot reductive carbonylation of 2-nitrophenols or 2-nitroanihne in the presence of selenium as catalyst. Besides the effect of base, the effects of solvent and temperature on the reaction were investigated at high or atmospheric pressure. Contrasting results were obtained for 2-benzoxazolones or 2-benzimidazolone at high and atmospheric pressures. Moreover, phase-transfer catalysis was exhibited. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

The carbenoid approach to peptide synthesis

A different approach to the synthesis of dipeptides is described based on the formation of the (NHCHRCONH)-C-1-(CHRCO)-C-2 bond by carbenoid N-H insertion, rather than the formation of the peptide bond itself. Thus decomposition of triethyl diazophosphonoacetate catalysed by rhodium(Ii) acetate in the presence of N-protected amino acid amides 8 gives the phosphonates 9, Subsequent Wadsworth-Emmons reaction of 9 with aldehydes in the presence of DBU gives dehydro dipeptides 10. The reaction has been extended to a simple two-step procedure, without the isolation of the intermediate phosphonate. for conversion of a range of amino acid amides 11 into dehydro dipepides 12 and to an N-methylamide 11h, and for conversion of a dipeptide: to tripeptide (13-14). Direct conversion, by using methyl diazophenylacetate, of amino acid amides to phenylglycine-containing dipeptides 19 proceeds in good chemical yield, but with poor diastereoselectivity.

A new approach to peptide synthesis

A new approach to the synthesis of dipeptides is described based on the formation of the CONH-CHRCO bond by carbenoid N-H insertion, rather than the formation of the peptide bond itself. The key N-H insertion reaction was carried out by treating a mixt. of N-protected amino acid amide and tri-Et diazophosphonoacetate, EtO2CC(:N2)PO(OEt)2, with a catalytic amt. of Rh2(OAc)4 in toluene to form phosphonates, e.g. I (R1 = H, Me, iso-Pr, iso-Bu; R2 = PhCH2O2C, Me3CO2C) in good yield. Dehydro dipeptides, e.g. II (R1, R2 = same as above; R3 = Ph, iso-Pr, N-Boc-indol-3-yl) were prepd. by Wadsworth-Emmons reaction of the phosphonates I with R3CHO using DBU as base.

X=Y-ZH COMPOUNDS AS POTENTIAL 1,3-DIPOLES .43. METAL-ION CATALYZED ASYMMETRIC 1,3-DIPOLAR CYCLOADDITION REACTIONS OF IMINES AND MENTHYL ACRYLATE

Metallo-azomethine ylides, generated from imines by the action of amine bases in combination with LiBr or AgOAc, undergo cycloaddition with both 1R, 2S, 5R- and 1S, 2R, 5S-menthyl acrylate at room temperature to give homochiral pyrrolidines in excellent yield. The stronger the base the faster the cycloaddition and the greater the yield with: 2-t-butyl-1,1,3,3-tetramethylguanidine > DBU > NEt(3) X-Ray crystal structures of representative cycloadducts establish that the absolute configuration of the newly established pyrrolidine stereocentres is independent of the metal salt and the size of the pyrrolidineC(2)-substituent for a series of aryl and aliphatic imines.

Bis-and tris (amidine) fluoroboron cations and related systems studies by Multinuclear NMR and fast atom bombardment mass spectometry

The formation and the isolation of fluoroboron salts, (D2BF2+)(PF6-), (DD'BF2+)(PF6-) and (D3BF2+)(PF6-)2, have been carried out. 1,8-Diazabicyclo [5,4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4,3,O]non-5-ene (DBN), extremely strong organic bases, were introduced into the fluoroboron cation systems and induced a complicated redistribution reaction in the D/BF3/BC13 systems. The result was the formation of all BFnCI4-n-, D.BFnCI3-n and fluoroboron cation species which were detected by 19p and 11B NMR spectrometry. The displacement reaction of CI- from these D.BFnCI3-n (n = 1 and 2) species by the second entering ligand is much faster than in other nitrogen donor containing systems which have been previously studied. Tetramethylguanidine, oxazolines and thiazolines can also produce similar reactions in D/BF3/BCI3 systems, but no significant BFnC4-n- species were observed. As well as influences of their basicity and their steric hindrance, N=C-R(X) (X = N, 0 or S) and N=C( X)2 (X = N or S) structures of ligands have significant effects on the fonnationof fluoroboron cations and the related NMR parameters. D3BF2+ and some D2BF2+ show the expected inertness, but (DBU)2BF2+ shows an interestingly high reactivity. (D2BF2+)(X-) formed from weak organic bases such as pyridine can react with stronger organic bases and form DD'BF2+ and D'2BF2+ in acetone or nitromethane. Fast atom bombardment mass spectrometry is doubly meaningful to this work. Firstly, FABMS can be directly applied to the complicated fluoroboron cation containing solution systems as an excellent complementary technique to multinuclear NMR. Secondly, the gas-phase ion substitution reaction of (D2BF2+)(PF6-) with the strong organic bases is successfully observed in a FABMS ion source when the B-N bond is not too strong in these cations.

Entwicklung eines Online-Messverfahrens zur Bestimmung des Bodenbedeckungsgrades bei der Stoppelbearbeitung zu Mulchsaatverfahren

Die vorliegende Arbeit ist Teil eines Verbund-Forschungsprojektes mit dem Ziel, eine Präzisions-Bodenbearbeitung in Abhängigkeit von verschiedenen Bodenparametern sowie dem Bodenbedeckungsgrad zu realisieren. Ziel dieses Teilprojektes war die Bereitstellung einer Online-Messung des Bedeckungsgrades, um die Bearbeitungsintensität während der Feldüberfahrt regeln zu können: Ein Kamerasensor vorne am Schlepper ermittelt die Bodenbedeckung und ein Tiefen-Sollwert wird an das Regelsystem eines Gerätes zur teilfächenspezifischen Bodenbearbeitung ausgegeben. Da unter Feldbedingungen Methoden zur Bedeckungsgradmessung nur relativ zueinander verglichen werden können, wurde zunächst ein Laborvergleich mit wohldefinierten Bodenbedeckungen durchgeführt, um die prinzipiellen Stärken und Schwächen von Bildanalyse sowie zwei visuellen Methoden (Gitterraster-Methode und „Meterstick-Methode“) zu ermitteln: • Eine visuelle Methode, die auf einer begrenzten Anzahl von einfachen Stichprobenbeobachtungen beruht (Gitter), überschätzte den Bedeckungsgrad systematisch, wobei dieser Effekt unter Feldbedingungen vermutlich klein gegenüber der bekannten Schwankungsbreite zwischen Messungen verschiedener Beobachter ist. • Eine visuelle Methode, die auch Größe und Orientierung des Strohs berücksichtigt (Meterstick), lieferte präzise mittlere Messwerte. Diese Methode war die mit Abstand arbeitsaufwändigste. • Nach einer einfachen Korrektur des Abbildungsfehlers des Kameraobjektivs war auch die Bildverarbeitungs-Methode in der Lage, die bekannten tatsächlichen Bedeckungsgrade exakt darzustellen, bei gleichzeitig der geringsten Schwankungsbreite der Messwerte. Die Online-Messung der Bodenbedeckung durch Ernterückstände ist bisher jedoch ungelöst. Obwohl in früheren Untersuchungen Texturmerkmale oder Farbunterschiede erfolgreich genutzt wurden, um den Bedeckungsgrad zu bestimmen, wird eine Bedienperson zur interaktiven Festlegung bestimmter Parameter benötigt. Um den Prototypen eines onlinefähigen Kamerasensors zu entwickeln, wurden geeignete Ausrüstung und Bedingungen zur Bildaufnahme untersucht und verschiedene Auswertealgorithmen mit Hilfe einer wissenschaftlichen Bildanalysesoftware geschrieben und getestet: • Da im Nahinfraroten zwischen ca. 800 und 1400 nm der größte Intensitäts-Kontrast zwischen Stroh und Boden besteht wurde zur Bildaufnahme eine Schwarz-Weiss-CCD-Kamera mit aufgesetztem Infrarotfilter gewählt. Eine Diffusor-Box sorgte für homogene Beleuchtungsbedingungen. • Zwei auf Kantendetektion und automatischer Schwellwertsetzung basierende Versionen („A“ und „B“) eines „klassischen“ Segmentierungsalgorithmus wurden geschrieben. Durch einen iterativen Ansatz konnten geeignete Thresholding-Verfahren abhängig von der Größenordnung der Bodenbedeckung verwendet werden. Die zur Online-Regelung der Bearbeitungstiefe nötige Beschränkung der Prozesslaufzeit auf ca. 1000 ms/Bild konnte eingehalten werden. • Eine alternative automatisierbare Kontrollmethode wurde entwickelt, welche Merkmale der Grauwerthistogramme der Stroh/Boden-Bilder auswertet (Algorithmus „C“). Dieser Ansatz ist nochmals deutlich schneller als eine Bildsegmentierung (ca. 5 – 10 Bilder/s). • Der Sensor wurde an einem Quad montiert und die Bodenbedeckung auf drei Testfeldern untersucht. Zwischen den Messergebnissen eines Algorithmus vom Typ A/B und dem Ansatz C wurde eine Pearson-Korrelation von 0,967 für die Messwertegesamtheit gefunden. • Auf Versuchsparzellen mit definiert aufgebrachten Strohmengen (ein weiteres Teil-projekt) wurden an GPS-referenzierten Punkten Bilder mit dem Sensor aufgenommen und Referenzmessungen mit der visuellen Gitterraster-Methode durchgeführt. Zwischen der Bildverarbeitung (A, B) und dem Gitter ergaben sich befriedigende Pearson-Korrelationen im Bereich von 0,7 – 0,8. Allerdings waren für hohe Bedeckungen die Ergebnisse des Sensors meist signifikant niedrigere als der Mittelwert von drei das Gitter auszählenden Personen. Eine Kontrolle mit Ansatz C ergab, dass die Histogramm-Merkmale der einzelnen Bilder deutlich besser mit den per Bildverarbeitung ermittelten Bedeckungsgraden korrelierten als mit den Gittermessungen. – Insgesamt erwies sich die schnelle Bildverarbeitung als geeignet für den Einsatz als neue Referenzmethode zur Messung der Bodenbedeckung durch Ernterückstände. • Da der Aufbau des Sensors ohne die Diffusor-Box praxisgerechter ist, besteht weiterer Forschungsbedarf in Bezug auf die dann auftretenden Probleme durch stark wechselnde Beleuchtung und Schattenwurf. • In einem letzten Schritt wurde der Kamerasensor erfolgreich in ein bereits entwickeltes System zur teilflächenspezifischen Bodenbearbeitung an der Universität Kiel integriert. Eine Regelung der Arbeitstiefe durch den Kamerasensor war problemlos möglich, allerdings gilt es noch belastbare Kriterien für die Vorgabe von Tiefen-Sollwerten in Abhängigkeit vom Bedeckungsgrad zu entwickeln.