Characterization of the Reaction Products of Hydrazine & Phenylhydrazine with Coba1t(II)

Total Page:16

File Type:pdf, Size:1020Kb

Characterization of the Reaction Products of Hydrazine & Phenylhydrazine with Coba1t(II) Indian Journal of Chemistry Vol. 23A, December 1984, pp. 1044-1045 Characterization of the Reaction following the procedure given by Domnin et al.13 Products of Hydrazine & Phenylhydrazine [m.p.60° (lit. m.p. 59.5-60SC]. Acetylacetonemono- with Coba1t(II), Nickel(II) & Zinc(II) hydrazone schilT base complexes of Co(lI), Ni(II) and Acetylacetonates Zn(II) were prepared as follows: About 0.4 ml of hydrazine hydrate in 10 ml of methanol was added dropwise with constant stirring to a suspension of 1.5 g R C AGGARWAL" & D S SURYA NARAYANA of the hydrated metal(II) acetylacetonate in 30 ml of Department of Chemistry, methanol and heated slowly on a water-bath upto Banaras Hindu University, Yaranasi 221005. 40°C until the suspension was completely dissolved. Received 16 March 1984; revised and accepted 25 June 1984 The complexes, which precipitated on vigorous stirring Complexes of the types M(AcHzh and M(acach(PHzh [M for further 15 min, were suction-filtered, washed with = Co(ll), Ni(ll) or Zn(II); AcHzH = acetylacetone monohydrazone; warm methanol and dried in vacuo. The phei:ylhydra- acacH = acetylacetone and PHz = phenylhydrazine] have been zine complexes were prepared by mixing and stirring prepared by the reactions of hydrazine and phenylhydrazine the methanolic solutions of phenylhydrazine and the respectively with metal(II) acetylacetonates. The complexes have metal(II) acetylacetonate in ~ 2: 1 molar ratio. The been characterised by elemental analyses, molar conductivity, magnetic susceptibility, electronic and IR spectral studies. The complexes, which precipitated almost immediately, magnetic moment and electronic spectral data suggest octahedral were suction-filtered, washed with methanol and dried stereochemistry for Co(II) and Ni(II) complexes. IR spectra indicate in vacuo over cone. H2S04, Prolonged heating or bridging bidentate and monodentate behaviours ofN - N moiety in refluxing of the reaction mixtures containing hydrazine M(AcHzh and M(acach(PHzh type of complexes respectively. or phenylhydrazine resulted in the formation of compounds of indefinite compositions. Although literature is replete with examples of The analytical data of the schilT base complexes transition metal complexes of bis(acetylacetone)di- (Table 1) suggest that two molecules of hydrazine react amine ligands!" 5, relatively few complexes have been with one molecules of metal(ll) acetylacetonate. The reported with ligands derived from the condensation of analytical data also show the formation of 1: 2 addition acetylacetone wth only one end of the diamine":", The complexes with phenylhydrazine. While AcHz reactions of transition metal(II) acetylacetonates with complexes ofCo(II), Ni(II) and ZnOI) melt at 166',205 different chelating ligands containing at least one NH2 and 189'C respectively and are soluble in non-polar group have also been studied":". Recently, Datta and solvents like methanol, ethanol etc., all the coworkers!" have shown that the reactions of phenylhydrazine complexes melt with decomposition VO(acach with benzoylhydrazine .and related ligands above 250C and are insoluble in the above solvents. yield two types of schilT base complexes: one involving However, all the complexes are freely soluble in polar the condensation ofvanadyl oxygen and the other that solvents like DMF or DMSO. The molar conductance of the carbonyl oxygen of the acetylacetonate ring. No values of the complexes in DMF (10-3 M solutions) work appears to have been done on the reactions of fall in the range 3.76-8.42 mhos em? mol- I suggesting hydrazine and phenylhydrazine with metal(II) the non-ionic nature of all the complexes under acetylacetonates. A study of the reactions of the above discussion". The Il", values of CoOl) and Ni(I1) hydrazines with Co(ll), Ni(II) and Zn(ll) acetylaceto- complexes (4.98-5.02 and 3.04-3.10 B.M. respectively) nates was therefore undertaken and the results are consistent with spin-free octahedral geometry obtained are discussed in this note. around these metal ions I 5. All the chemicals used in the present work were An intense band in the region 31,250-31,746 ern I of BDH reagents or of equivalent grade. Hydrazine the UV spectra of M(AcHzh type complexes and a hydrate and phenylhydrazine were distilled twice band in the region 31,545-32,895 cm - I of the spectra of before use. Hydrated metal(l I) acetylacetonates were M(acach(PHzh type complexes is attributed to a 1[-1[* prepared as described in literature I I. Ex perimental transition due to the pscudoaromaticity of cnamine details pertaining to elemental analyses, molar and acetylacetonate ring respectively present in conductivity, magnetic susceptibility, electronic and IR them'2.'6 spectral studies were similar to those described in our The electronic spectra of Co(ll) complexes arc earlier paper 12 consistent with an octahedral stereochemistry as they AcHzH was prepared from the ice-cold ethanolic show two J-J bands at 8.772-9,346 and 18,519- solutions of hydrazine hydrate and acetylacetone 20,408cm I which can be assigned to 4T2y 1044 NOTES Table I-Analytical, Magnetic and Electronic Spectral Data of the Complexes pc Compound Colour Found (Calc.), % Ileff. Dq B IJ LFSE I L (B.M.) (em -I) (cm- ) ( '/~) (kJmol- ) Metal N Co(AcHzh Pink 20.45 19.46 4.98 995.4 854.5 0.879 12.1 95.26 (20.68) (19.65) Cotacac), (PHzh Pinkish 12.21 11.58 5.02 1043.9 684.4 0.704 29.6 99.9 brown (12.46) (11.84) Ni(AcHzh Blue 20.21 19.43 3.10 985.2 932.8 0.896 10.4 141.42 (20.62) (19.67) Ni(acach(PHzh Greenish 12.33 11.63 3.04 995.0 806.1 0.774 22.6 142.83 blue (12.42) (11.85) Zn(AcHzh Greenish 22.04 18.98 white (22.44) (19.22) Zn(acach(PHzh Light 13.18 11.39 yellow (13.64) (11.68) ) complexes are assigned to perturbed carbonyl and (C..:...:..:. .-4TI9(F)(vl and 4T1g(P).-4T1g(F)(h) transitions respectively!" The spectra of Ni(II) complexes yield C)/(C..:...:..:.N)stretching vibrations respectively 16.1 9. The three d-d bands at 9,852-9,950, 15,980-16,130 and non-ligand bands obtained in the regions 430-410 and 22,270-23,510 cm - 1 assignable to the transitions 310-268 em -I in the spectra of M(AcHz}z and arising from 3 Azg ground state to 3Tzg(v1), 3TI9(F)(vz) M(acac)z(PHz}z type complexes respectively are and 3 T1g(P)(V3) excited states respectively. The assigned to v(M - 0) mode while those obtained in the positions and assignments of the banlis indicate region 258-227 cm - 1 in the spectra of all the complexes octahedral environment around the nickel(II)I? The under discussion are assigned to v(M - N) modezo.zl. p0 values of Co(ll) and Ni(II) complexes (Table1) References indicate maximum covalency of 12.1 and 29.6 percent 1 Holm R H, Everett (Jr) G W & Chakravorty A, Prog inorg Chern, in M(AcHz}z and phenylhydrazine complexes 7 (1966) 83. respectively. 2 Bong-II Kim, Chi Miyake & Imoto S,) inorg nucl Chern, 37 (1975) 963. The nujol mull spectrum of acetylacetonemono- 3 Biradar N S & Locker A L,) inorg nucl Chern, 37 (1975) 1308. hydrazone gives a broad band in the region 3500- 4 Rana V B. Singh P, Singh D P & Teotia M p, Polyhedron, 1 (1982) 377. 3000 em - 1 probably due to the presence of inter- and 5 Aggarwal R C & Surya Narayana D S, Indian) Chern, (accepted). intra-molecular hydrogen bonding between the OH 6 Wallis W N & Cummings S C, Inorg Chern, 13 (1974) 991. and NHjNHz groups of the ligand. Replacement of 7 Costes J P, Cross G, Donbien M H & Laurent J P, Inorg chim this broad band by two well-defined bands in the Acta, 60 (1982) 111. regions 3320-3310 and 3185-3180 ern - 1 in the spectra 8 Dey K, Maiti R K & Sen S K. Inorg chirn Acta. 20 (1976) 197. 9 Mathis A A D. Snow M R & Vanzo J A. Chern Cornrnun, 7 (1976) of its complexes suggests the presence of NHz group 264. and absence of OH group in the complexes. The v(N 10 Datta R L & Pal A K. Indian) Chern, 21A (1982) 1130. - N) band observed at 888 cm - 1 in the' spectrum of II Fackler (Jr) J P. Prog inorg Chern. 7 (1966) 361. acetylacetone monohydrazone is shifted to the region 12 Aggarwal R C, Surya Narayana D S & Sekhar V C, Indian) 980-958 em - 1 in the spectra of M(AcHzh complexes. A Chern. 21A (1982) 419. 13 Dornnin N A. Syui-Kun Van & Glcbovskaya N S. Zhur obsch 'positive shift of 70-92 ern - 1 in the above mode Khirn. 27 (1957) 1512: Chern Abstr. 52 (1957) 37014. provides a strong evidence for the bridging bidentate 14 Geary W J. Coord Chern Rt'l". 7 (1971) 81. nature of the N - N moiety of the ligand 1 B. 15 Cotton F A & Wilkinson G. Adranced inorganic Chemistry. Phenylhydrazine gives a broad band in the region (Wiley. New York) 1976.916. 34()()-3250 cm - I and a weak band at 3090 cm - 1 due to 16 Cumnings S C & Sievers R E.lnorg Chern. 9 (1970) 1131. NH/NHz groups and these bands are shifted to lower 17 Lever A B P. Inorganic electronic spectroscopy (Elsevier. frequencies (3390, 3195 and 3040 cm - I) in the Amsterdam) 1968. 324. 334. 18 Braibanti A. Dallawalle F. Pellingheli M A & Leaporathi E. complexes. indicating the coordination of phenyl- l norg Chem.
Recommended publications
  • Synthesis and Antimicrobial Evaluation of Some Novel Thiazole, Pyridone, Pyrazole, Chromene, Hydrazone Derivatives Bearing a Biologically Active Sulfonamide Moiety
    Int. J. Mol. Sci. 2014, 15, 1237-1254; doi:10.3390/ijms15011237 OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article Synthesis and Antimicrobial Evaluation of Some Novel Thiazole, Pyridone, Pyrazole, Chromene, Hydrazone Derivatives Bearing a Biologically Active Sulfonamide Moiety Elham S. Darwish *, Azza M. Abdel Fattah, Fawzy A. Attaby and Oqba N. Al-Shayea Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt; E-Mails: [email protected] (A.M.A.F.); [email protected] (F.A.A.); [email protected] (O.N.A.-S.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +20-100-588-1771; Fax: +202-570-8480. Received: 10 November 2013; in revised form: 10 January 2014 / Accepted: 13 January 2014 / Published: 17 January 2014 Abstract: This study aimed for the synthesis of new heterocyclic compounds incorporating sulfamoyl moiety suitable for use as antimicrobial agents via a versatile, readily accessible N-[4-(aminosulfonyl)phenyl]-2-cyanoacetamide (3). The 2-pyridone derivatives were obtained via reaction of cyanoacetamide with acetylacetone or arylidenes malononitrile. Cycloaddition reaction of cyanoacetamide with salicyaldehyde furnished chromene derivatives. Diazotization of 3 with the desired diazonium chloride gave the hydrazone derivatives 13a–e. Also, the reactivity of the hydrazone towards hydrazine hydrate to give Pyrazole derivatives was studied. In addition, treatment of 3 with elemental sulfur and phenyl isothiocyanate or malononitrile furnished thiazole and thiophene derivatives respectively. Reaction of 3 with phenyl isothiocyanate and KOH in DMF afforded the intermediate salt 17 which reacted in situ with 3-(2-bromoacetyl)-2H-chromen-2-one and methyl iodide afforded the thiazole and ketene N,S-acetal derivatives respectively.
    [Show full text]
  • Feiii, Cuii and Znii Complexes of the Rigid 9-Oxido-Phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties
    International Journal of Molecular Sciences Article FeIII, CuII and ZnII Complexes of the Rigid 9-Oxido-phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties Katharina Butsch 1, Alexander Haseloer 1 , Simon Schmitz 1, Ingo Ott 2, Julia Schur 2 and Axel Klein 1,* 1 Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, D-50939 Köln, Germany; [email protected] (K.B.); [email protected] (A.H.); [email protected] (S.S.) 2 Institute of Medicinal and Pharmaceutical Chemistry, Technische Universität Braunschweig, Beethovenstrasse 55, D-38106 Braunschweig, Germany; [email protected] (I.O.); [email protected] (J.S.) * Correspondence: [email protected] Abstract: The three complexes [Fe(opo)3], [Cu(opo)2], and [Zn(opo)2] containing the non-innocent anionic ligand opo− (opo− = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthe- 1 sised from the corresponding acetylacetonates. [Zn(opo)2] was characterised using H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)3] and [Cu(opo)2] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)2] and [Cu(acac)2] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)3] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)3] in − Citation: Butsch, K.; Haseloer, A.; THF (Hacac = acetylacetone, 2,4-pentanedione; acac = acetylacetonate). The narrow, completely Schmitz, S.; Ott, I.; Schur, J.; Klein, A. isotropic signal of [Fe(opo)3] disagrees with a metal-centred S = 5/2 spin system that is observed FeIII, CuII and ZnII Complexes of the in the solid state.
    [Show full text]
  • Glycosyl Barbiturate Ligands of Bacterial Lectins: from Monomer Design to Glycoclusters and Glycopolymers François Portier, Anne Imberty, Sami Halila
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Archive Ouverte en Sciences de l'Information et de la Communication Expeditious Synthesis of C -Glycosyl Barbiturate Ligands of Bacterial Lectins: From Monomer Design to Glycoclusters and Glycopolymers François Portier, Anne Imberty, Sami Halila To cite this version: François Portier, Anne Imberty, Sami Halila. Expeditious Synthesis of C -Glycosyl Barbiturate Lig- ands of Bacterial Lectins: From Monomer Design to Glycoclusters and Glycopolymers. Bioconjugate Chemistry, American Chemical Society, 2019, 30 (3), pp.647-656. 10.1021/acs.bioconjchem.8b00847. hal-02322076 HAL Id: hal-02322076 https://hal.archives-ouvertes.fr/hal-02322076 Submitted on 4 Aug 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. EXPEDITIOUS SYNTHESIS OF C‐GLYCOSYL BARBITURATE LIGANDS OF BACTERIAL LECTINS: FROM MONOMER DESIGN TO GLYCOCLUSTERS AND GLYCOPOLYMERS François Portier, Anne Imberty and Sami Halila* Univ. Grenoble Alpes, CNRS, CERMAV, 38000 Grenoble, France. E‐mail: [email protected]; Fax: +33 4 76 54 72 03; Tel : +33 4 76 03 76 66 ABSTRACT The approach developed here offers a straightforward and efficient access to ‐C‐glycosyl barbiturates ligands, spanning from glycomimetics to multivalent C‐neoglycoconjugates, with the aim of deciphering structural parameters impacting the binding to pathogenic lectins.
    [Show full text]
  • Effect of the Titanium Isopropoxide:Acetylacetone Molar Ratio on the Photocatalytic Activity of Tio2 Thin Films
    molecules Article Effect of the Titanium Isopropoxide:Acetylacetone Molar Ratio on the Photocatalytic Activity of TiO2 Thin Films Jekaterina Spiridonova 1,* , Atanas Katerski 1, Mati Danilson 2 , Marina Krichevskaya 3,* , Malle Krunks 1 and Ilona Oja Acik 1,* 1 Laboratory of Thin Films Chemical Technologies, Department of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia; [email protected] (A.K.); [email protected] (M.K.) 2 Laboratory of Optoelectronic Materials Physics, Department of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia; [email protected] 3 Laboratory of Environmental Technology, Department of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia * Correspondence: [email protected] (J.S.); [email protected] (M.K.); [email protected] (I.O.A.); Tel.: +372-620-3369 (I.O.A.) Academic Editors: Smagul Karazhanov, Ana Cremades and Cuong Ton-That Received: 31 October 2019; Accepted: 25 November 2019; Published: 27 November 2019 Abstract: TiO2 thin films with different titanium isopropoxide (TTIP):acetylacetone (AcacH) molar ratios in solution were prepared by the chemical spray pyrolysis method. The TTIP:AcacH molar ratio in spray solution varied from 1:3 to 1:20. TiO2 films were deposited onto the glass substrates at 350 ◦C and heat-treated at 500 ◦C. The morphology, structure, surface chemical composition, and photocatalytic activity of the obtained TiO2 films were investigated. TiO2 films showed a transparency of ca 80% in the visible spectral region and a band gap of ca 3.4 eV irrespective of the TTIP:AcacH molar ratio in the spray solution.
    [Show full text]
  • Synthesis and Characterization of Schiff Bases Derived from Acetylacetone and Their Theoretical Study
    International Journal of ChemTech Research CODEN( USA): IJCRGG ISSN : 0974-4290 Vol.5, No.1, pp 204-211, Jan-Mar 2013 Synthesis And Characterization Of Schiff Bases Derived From Acetylacetone And Their Theoretical Study Adnan dib Department of Chemistry, Faculty of Science, Laboratory of Organic Chemistry, University of Damascus, Syria Corres.author: [email protected] Abstract: Schiff basesderived from acetylacetone were synthesized and characterized by Ms, IR, 1H ,13C NMR and element analysis. Hyper Chem-6 program has been used to predict structural geometries of compounds in gas phase. The heat of formation (ΔHf º) and binding energy (ΔEb) at 298 ºK for the free ligand was calculated by PM3 method. Keywords: Schiff bases, acetylacetone, hydrazine, PM3 method. Introduction Experimental Schiff bases are one of the most versatile classes of Reagents and Apparatus. ligands for the study of the coordination of transition All the chemicals used were of AnalaR grade and metals[1]. Their ease of synthesis (by the procured from Sigma-Aldrich and Fluka. Metal salts condensation of an aldehyde/ketone with an amine), were purchased from E. Merck and were used as multidenticity (from mono to hexadentate), received. Distilled water was used in extraction combination of donor atoms (coordination usually experimentals. The solvents were saturated with through the imine nitrogen and other atoms like each other before use in order to prevent volume oxygen, sulfur or nitrogen) and stability have made changes of the phases during extraction. The C, H, them the preferred ligand system in catalysis, and N were analyzed on a Carlo-Erba 1106 biological modeling, the design of molecular elemental analyzer.
    [Show full text]
  • Determination of Solvent Effects on Ketoðenol Equilibria of 1,3-Dicarbonyl Compounds Using NMR: Revisiting a Classic Physical C
    In the Laboratory Determination of Solvent Effects on Keto–Enol Equilibria W of 1,3-Dicarbonyl Compounds Using NMR Revisiting a Classic Physical Chemistry Experiment Gilbert Cook* and Paul M. Feltman Department of Chemistry, Valparaiso University, Valparaiso, IN 46383; *[email protected] “The influence of solvents on chemical equilibria was discovered in 1896, simultaneously with the discovery of keto–enol tautomerism in 1,3-dicarbonyl compounds” (1). The solvents were divided into two groups according to their ability to isomerize compounds. The study of the keto–enol tautomerism of β-diketones and β-ketoesters in a variety of solvents using proton NMR has been utilized as a physical Figure 1. The β-dicarbonyl compounds studied in the experiment. chemistry experiment for many years (2, 3). The first reported use of NMR keto–enol equilibria determination was by Reeves (4). This technique has been described in detail in an experiment by Garland, Nibler, and Shoemaker (2). panded (i) to give an in-depth analysis of factors influencing The most commonly used β-diketone for these experi- solvent effects in tautomeric equilibria and (ii) to illustrate ments is acetylacetone (Scheme I). Use of proton NMR is a the use of molecular modeling in determining the origin of viable method for measuring this equilibrium because the a molecule’s polarity. The experiment’s original benefits of tautomeric keto–enol equilibrium is slow on the NMR time using proton NMR as a noninvasive method of evaluating scale, but enol (2a)–enol (2b) tautomerism is fast on this scale equilibrium are maintained. (5). It has been observed that acyclic β-diketones and β- Experimental Procedure ketoesters follow Meyer’s rule of a shift in the tautomeric equi- librium toward the keto tautomer with increasing solvent Observations of the solvent effects for three other 1,3- polarity (6).
    [Show full text]
  • Acetylacetone
    Safety data sheet acc. to Safe Work Australia - Code of Practice Acetylacetone ≥98 %, for synthesis article number: 6716 date of compilation: 2016-11-08 Version: GHS 2.0 en Revision: 2021-06-11 Replaces version of: 2016-11-08 Version: (GHS 1) SECTION 1: Identification of the substance/mixture and of the company/ undertaking 1.1 Product identifier Identification of the substance Acetylacetone ≥98 %, for synthesis Article number 6716 CAS number 123-54-6 Alternative name(s) Pentane-2,4-dione 1.2 Relevant identified uses of the substance or mixture and uses advised against Relevant identified uses: Laboratory chemical Laboratory and analytical use Uses advised against: Do not use for products which come into contact with foodstuffs. Do not use for private purposes (household). 1.3 Details of the supplier of the safety data sheet Carl Roth GmbH + Co KG Schoemperlenstr. 3-5 D-76185 Karlsruhe Germany Telephone:+49 (0) 721 - 56 06 0 Telefax: +49 (0) 721 - 56 06 149 e-mail: [email protected] Website: www.carlroth.de Competent person responsible for the safety data :Department Health, Safety and Environment sheet: e-mail (competent person): [email protected] 1.4 Emergency telephone number Name Street Postal Telephone Website code/city NSW Poisons Information Centre Hawkesbury Road 2145 West- 131126 Childrens Hospital mead, NSW SECTION 2: Hazards identification 2.1 Classification of the substance or mixture Classification acc. to GHS Section Hazard class Cat- Hazard class and Hazard egory category statement 2.6 Flammable liquid 3 Flam. Liq. 3 H226 3.1O Acute toxicity (oral) 4 Acute Tox.
    [Show full text]
  • Polarography As a Measure of Ionic Environment
    University of the Pacific Scholarly Commons University of the Pacific Theses and Dissertations Graduate School 1965 Polarography As A Measure Of Ionic Environment James Wilburne Larsen University of the Pacific Follow this and additional works at: https://scholarlycommons.pacific.edu/uop_etds Part of the Chemistry Commons Recommended Citation Larsen, James Wilburne. (1965). Polarography As A Measure Of Ionic Environment. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/2881 This Dissertation is brought to you for free and open access by the Graduate School at Scholarly Commons. It has been accepted for inclusion in University of the Pacific Theses and Dissertations by an authorized administrator of Scholarly Commons. For more information, please contact [email protected]. .. i:' ~)~-~;~::"',:'.,·~-~ -~·-:.·: ~ -~ ·. ,. '~:-··~· ··:.\';~<_; i ~~ .:•i'{O" .1"' POLAROGRAPHY AS A MEASURE OF IONIC ENVIRONMENT A Dissertation _Presented to the Faculty of the Graduate School University of the Pacific In Partial Fulfillment of the Requirements for the Degree (f ' Doctor of Philosophy by James Wilburne Larsen June 1965 This disseljtatic;m,, written apd submitted by is approved for recornrnendat,ipn to the Graduate Co~ncil, University of th~ P~(::.ific • . D~partmept Chairwan or Dean: ACKNOWLEDGEMENTS The writer wishes to express his appreciation to the faculty of the Chemistry Department for their assistance, especially Dr. Herschel Frye for his criticisms and guidance. TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION
    [Show full text]
  • Biosynthesis of Acetylacetone Inspired by Its Biodegradation
    Zhou et al. Biotechnol Biofuels (2020) 13:88 https://doi.org/10.1186/s13068-020-01725-9 Biotechnology for Biofuels RESEARCH Open Access Biosynthesis of acetylacetone inspired by its biodegradation Yifei Zhou1,2, Yamei Ding3, Wenjie Gao1, Jichao Wang1, Xiutao Liu1,2, Mo Xian1, Xinjun Feng1* and Guang Zhao1,4* Abstract Background: Acetylacetone is a commercially bulk chemical with diverse applications. However, the traditional manufacturing methods sufer from many drawbacks such as multiple steps, harsh conditions, low yield, and environ- mental problems, which hamper further applications of petrochemical-based acetylacetone. Compared to conven- tional chemical methods, biosynthetic methods possess advantages such as being eco-friendly, and having mild conditions, high selectivity and low potential costs. It is urgent to develop biosynthetic route for acetylacetone to avoid the present problems. Results: The biosynthetic pathway of acetylacetone was constructed by reversing its biodegradation route, and the acetylacetone was successfully produced by engineered Escherichia coli (E. coli) by overexpression of acetylac- etone-cleaving enzyme (Dke1) from Acinetobacter johnsonii. Several promising amino acid residues were selected for enzyme improvement based on sequence alignment and structure analysis, and the acetylacetone production was improved by site-directed mutagenesis of Dke1. The double-mutant (K15Q/A60D) strain presented the highest acetylacetone-producing capacity which is 3.6-fold higher than that of the wild-type protein. Finally, the strain accu- mulated 556.3 15.2 mg/L acetylacetone in fed-batch fermentation under anaerobic conditions. ± Conclusions: This study presents the frst intuitive biosynthetic pathway for acetylacetone inspired by its biodegra- dation, and shows the potential for large-scale production.
    [Show full text]
  • Physical Chemical Studies on Inorganic Coordination Compounds. I. Metallic Complexes of Dimethylsulfoxide. II. Preparation and Spectral Studies of Vanadyl Complexes
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1961 Physical Chemical Studies on Inorganic Coordination Compounds. I. Metallic Complexes of Dimethylsulfoxide. II. Preparation and Spectral Studies of Vanadyl Complexes. Lawrence Henry Holmes Jr Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Holmes, Lawrence Henry Jr, "Physical Chemical Studies on Inorganic Coordination Compounds. I. Metallic Complexes of Dimethylsulfoxide. II. Preparation and Spectral Studies of Vanadyl Complexes." (1961). LSU Historical Dissertations and Theses. 713. https://digitalcommons.lsu.edu/gradschool_disstheses/713 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. This dissertation has been 62-1233 microfilmed exactly as received H O L M E S , Jr., Lawrence Henry, 1935- PHYSICAL CHEMICAL STUDIES ON INORGANIC COORDINATION COMPOUNDS. I. METALLIC COMPLEXES OF DIMETHYLSULFOXIDE. II. PRE­ PARATION AND SPECTRAL STUDIES OF VANA­ DYL COMPLEXES. University Microfilms, Inc., Ann Arbor, Michigan H O L M E S , Jr., Lawrence Henry, 193 5- 62-1233 Louisiana State University, Ph.D., 1961 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan PHYSICAL' CHEMICAL STUDIES ON INORGANIC COORDINATION COMPOUNDS I. METALLIC COMPLEXES OF DIMETHYIBULFOXIDE II. PREPARATION AND SPECTRAL STUDIES OF VANADYL COMPLEXES A DISSERTATION Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Ffechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Lawrence Henry Holmes, Jr.
    [Show full text]
  • Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium As Catalysts
    K. K. GEORGIEFF I Research Laboratories, Shawinigan Chemicals, Ltd., Shawinigan Falls, Quebec, Canada Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium as Catalysts Reduction in costs, hazards, and time of re- action makes this process commercially attractive 1NDUSTRIAL production of acetylacetone ester, length of time required to complete The yields with methyl acetone, which by the Claisen condensation of acetone the reaction, and effect of temperature on had been dried with acetic anhydride, and aliphatic acetate esters, using sodium yield are lacking. This information is were identical to those obtained with or sodium alkoxide as catalyst, has been given in the present article. The amount chemically pure synthetic mixtures of the made economically impossible by the of by-product acetoacetic ester produced same composition. hazards of the reaction, the low yields, in the author’s experiments was small as The inert diluent materially affected and the great length of time required compared to that divulged in the patent. the yield, but the amount was not crit- for reaction of the last few per cent of the This was probably due to a difference in ical within wide ranges of concentra- sodium, because of coating of the par- the amount of diluent used, although the tion. Best results were obtained with ticles. The latter disadvantage has, to a slightly different order of adding the re- medium boiling hydrocarbons such as small extent, been alleviated by use of so- agents may have had a minor effect. toluene. Isohexane gave somewhat called “sodium sand.” Within recent lower yields, while Varsol (a commercial years, dispersed sodium of 1- to 20- petroleum fraction, boiling point 154’ micron particle size has become commer- Sodium Alkoxide as Catalyst to 175’ C.) gave much poorer results.
    [Show full text]
  • Design, Synthesis and Docking Studies of Novel Thiazole Derivatives Incorporating Pyridine Moiety and Assessment As Antimicrobial Agents Rizk E
    www.nature.com/scientificreports OPEN Design, synthesis and docking studies of novel thiazole derivatives incorporating pyridine moiety and assessment as antimicrobial agents Rizk E. Khidre 1,2,3* & Ibrahim Ali M. Radini1,3 A novel series of substituted 4,6-dimethyl-2-oxo-1-(thiazol-2-ylamino)-1,2-dihydropyridine- 3-carbonitrile derivatives 6, 9, 13, 15, and 17 was synthesized in a good to excellent yield from the reaction of 1-(3-cyano-4,6-dimethyl-2-oxopyridin-1(2H)-yl)thiourea with 2-oxo-N’- arylpropanehydrazonoyl chloride, chloroacetone, α-bromoketones, ethyl chloroacetate, and 2,3-dichloroquinoxaline, respectively. The potential DNA gyrase inhibitory activity was examined using in silico molecular docking simulation. The novel thiazoles exhibit dock score values between − 6.4 and − 9.2 kcal/mol and they were screened for their antimicrobial activities. Compound 13a shown good antibacterial activities with MIC ranged from 93.7–46.9 μg/mL, in addition, it shown good antifungal activities with MIC ranged from 7.8 and 5.8 μg/mL. Tiazoles are present in numerous natural products e.g. epithilone, thiostrepton, thiamine pyrophosphate (TPP), carboxylase vitamin B1, and penicillin1. Tiazoles have diverse applications in drug development for treatment allergies2, infammation3, HIV infections4, hypertension5, bacterial infections 6, hypnotics7, schizophrenia8, and pain9, as novel inhibitors of bacterial DNA gyrase B10, and as fbrinogen receptor antagonists with antithrom- botic activity11. Tey exhibited fabulous pharmaceutical activities for instance antifungal 12, antimicrobial13–15, anti-infammatory16,17, analgesic18, and anti-cancer19,20, anticonvulsant activities 21. Tere are several commercial drugs contain thiazole moiety (Fig. 1). Pyridines are an important class of heterocyclic compounds because they occur in many natural compounds that have biological activity such as vitamin B3 (niacin) and vitamin B6 (pyridoxin) and natural alkaloids 22.
    [Show full text]