DOCSLIB.ORG

A Simpler Route to Building Photochromic Cinnamaldehyde Semicarbazones Byron R

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
A Simpler Route to Building Photochromic Cinnamaldehyde Semicarbazones Byron R Eastern Illinois University The Keep Masters Theses Student Theses & Publications 2015 A Simpler Route to Building Photochromic Cinnamaldehyde Semicarbazones Byron R. Ebbert Eastern Illinois University This research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out more about the program. Recommended Citation Ebbert, Byron R., "A Simpler Route to Building Photochromic Cinnamaldehyde Semicarbazones" (2015). Masters Theses. 1721. https://thekeep.eiu.edu/theses/1721 This is brought to you for free and open access by the Student Theses & Publications at The Keep. It has been accepted for inclusion in Masters Theses by an authorized administrator of The Keep. For more information, please contact [email protected]. The Graduate School~ EASTERN lWN(1!5 UNIVERSITY" Thesis Maintenance and Reproduction Certificate FOR: Graduate Candidates Completing Theses in Partial Fulfillment of the Degree Graduate Faculty Advisors Directing the Theses RE: Preservation, Reproduction, and Distribution of Thesis Research Preserving, reproducing, and distributing thesis research is an important part of Booth Library's responsibility to provide access to scholarship. In order to further this goal, Booth Library makes all graduate theses completed as part of a degree program at Eastern Illinois University available for personal study, research, and other not-for-profit educational purposes. Under 17 U.S.C. § 108, the library may reproduce and distribute a copy without infringing on copyright; however, professional courtesy dictates that permission be requested from the author before doing so. Your signatures affirm the following: • The graduate candidate is the author of this thesis. • The graduate candidate retains the copyright and intellectual property rights associated with the original research, creative activity, and intellectual or artistic content of the thesis. • The graduate candidate certifies her/his compliance with federal copyright law (Title 17 of the U. S. Code) and her/his right to authorize reproduction and distribution of all copyrighted materials included in this thesis. • The graduate candidate in consultation with the faculty advisor grants Booth Library the non­ exclusive, perpetual right to make copies of the thesis freely and publicly available without restriction, by means of any current or successive technology, including by not limited to photocopying, microfilm, digitization, or internet. • The graduate candidate acknowledges that by depositing her/his thesis with Booth Library, her/his work is available for viewing by the public and may be borrowed through the library's circulation and interlibrary loan departments, or accessed electronically. • The graduate candidate waives the confidentiality provisions of the Family Educational Rights and Privacy Act (FERPA) (20 U. S. C. § 1232g; 34 CFR Part 99) with respect to the contents of the thesis and with respect to information concerning authorship of the thesis, including name and status as a student at Eastern Illinois University. I have conferred with my graduate faculty advisor. My signature below indicates that I have read and agree with the above statements, and hereby give my permission to allow Booth Library to reproduce and distribute my thesis. My adviser's signature indicates concurrence to reproduce and distribute the thesis. Printed Name Printed Name Graduate Degree Program / Date 7 Please submit in duplicate. A Simpler Route to Building Photochromic Cinnamaldehyde Semicarbazones (TITLE) BY Byron R. Ebbert THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science in Chemistry IN THE GRADUATE SCHOOL, EASTERN ILLINOIS UNIVERSITY CHARLESTON, ILLINOIS 2015 YEAR I HEREBY RECOMMEND THAT THIS THESIS BE ACCEPTED AS FULFILLING THIS PART OF THE GRADUATE DEGREE CITED ABOVE THESIS COMMITTEE CHAIR DATE DEPARTMENT/SCHOOL CHAIR DATE OR CHAIR'S DESIGNEE oA?/.~8 /,Jv1 !.·­ THESIS COMMITTEE MEMBER DATE DATE DATE THESIS COMMITTEE MEMBER DATE A Simpler Route to Building Photochromic Cinnamaldehyde Semicarbazones by Byron R. Ebbert 1 Table of Contents Abstract .......................................................................................................................... 3 Acknowledgments .......................................................................................................... 5 List of Figures ................................................................................................................. 6 List of Tables ................................................................................................................... 8 List of 1 H NMR Spectra ................................................................................................... 9 List of Abbreviations Used ............................................................................................. 10 Introduction .................................................................................................................. 11 Results and Discussion ................................................................................................ 19 1. Preparation of semicarbazone starting materials ............................................... 19 2. Brominations of crotonaldehyde semicarbazone ............................................... 20 3. Brominations of 1-hexene and alkyl crotonates ................................................. 28 4. Bromination of 3-penten-2-one and N,N-dialkyl CSCs ...................................... 31 5. Bromination of various imines ............................................................................ 35 6. Arbuzov reaction of ethyl 4-bromocrotonate ...................................................... 39 Conclusions and Future Directions ............................................................................... 40 Experimental ................................................................................................................. 42 References ................................................................................................................... 62 Appendices 1H NMR Spectra for Selected Compounds ............................................................. 66 2 ABSTRACT Photochromic semicarbazones are an interesting group of compounds that show potential in a broad range of applications, including as a more environmentally friendly replacement for photochromic metal complex compounds. Previous work has shown the feasibility to synthesize photochromic cinnamaldehyde semicarbazones (CSCs) from a benzaldehyde and a protected acetaldehyde Wittig reagent. A new, quicker, and cheaper approach to constructing these CSCs from crotonaldehyde was explored in this research. A three reaction sequence would convert crotonaldehyde to a CSC; first, an allylic bromination of the semicarbazone with N-bromosuccinimide (NBS); second, an Arbuzov reaction to prepare the semicarbazone phosphonate; and finally a condensation of this phosphonate with a benzaldehyde. The first step of synthesizing crotonaldehyde semicarbazone was successfully achieved in a 97.2% yield (68.5% for the analogous thiosemicarbazone). However, over 20 attempts at the second step involving the allylic bromination of the semicarbazone were made, with various solvents, halogenation sources, radical initiators, reaction times and temperatures, but with no success. Each reaction yielded a complex mixture of several new compounds, none of which appeared to be the desired 4-bromocrotonaldehyde semicarbazone. The bromination conditions were proved viable by reaction of 1-hexene and methyl or ethyl crotonate with NBS or dibromodimethylhydantoin (DBDMH) to successfully give the bromine substituted product, although the use of DBDMH also led to dibrominated addition across the double bond with the crotonates. The products were confirmed by both 1H and 13C NMR and GC/MS analysis. The results suggested that the problem was in the semicarbazide substrate and not the reaction conditions. 3 With this in mind, additional crotonaldehyde analogs with various imino groups were synthesized and subjected to the same bromination conditions. To this end, methyl (2-butenylidene)hydrazinocarboxylate (49% yield), crotonaldehyde dinitrophenyl­ hydrazone (67% yield), and 2-cyclohexen-1-semicarbazone (44% yield) were synthesized. Bromination with NBS gave the desired product for the cyclohexenone substrate. However bromination of the methyl hydrazinocarboxylate gave a mixture of the allylic substitution product, the dibromide addition product, and a dimer. Reaction of the dinitrophenylhydrazone gave an allylic bromination product, but with the hydrazino group oxidized to an azo group and with migration of the double bond. These results suggest that the H off the imine carbon, and the NH in the hydrazine group, are responsible for preventing successful bromination of crotonaldehyde semicarbazone. Attempts were made to synthesize and brominate other crotonaldehyde analogs, such as the methylimine, the oxime (hydroxylimine), the cyclohexylimine, the hydrazone, and the 2-aminoethylimine. None of these starting materials were successfully prepared, either with traditional solution condition or with solventless techniques, and this is most likely due to the high solubility and instability of these compounds. To further test the route, the third step, phosphorylation of an allylic bromide, was carried out on ethyl 4-bromocrotonate with high yield (91.7%). There are many examples in the literature that
Load more

Recommended publications
  • The. Reactions Op Semicarbazones, Thiosbmicarbazonbs
    THE. REACTIONS OP SEMICARBAZONES, THIOSBMICARBAZONBS AMD RELATED COMPOUNDS, IMCLTJDIMG THE ACTION OF AMINES ON AMINOCARBOCARBAZONES. A THESIS PRESENTED BY JOHN MCLEAN B.So. IN FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY OF THE UNIVERSITY OF GLASGOW. / MAY *936. THE ROYAL TECHNICAL COLLEGE, GLASGOW. ProQuest Number: 13905234 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 13905234 Published by ProQuest LLC(2019). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 This research was carried out in the Royal Technical College, Glasgow, under the supervision of Professor F.J. Wilson, whose helpful advice was greatly appreciated by the author. CONTENTS. Page General Introduction, PART 1. The Action of Amines on Amino Carhocarbazones. Introduction... ..... ,..................... 4 Benzylamine......... Theoretical.............. 11 ......... Experimental............. 15 Aniline............. Theoretical............ 21 ............. Experimental............ 22 B-Naphthylamine..... Theoretical............... 27
    [Show full text]
  • Organic Chemistry/Fourth Edition: E-Text
    CHAPTER 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP O X ldehydes and ketones contain an acyl group RC± bonded either to hydrogen or Ato another carbon. O O O X X X HCH RCH RCRЈ Formaldehyde Aldehyde Ketone Although the present chapter includes the usual collection of topics designed to acquaint us with a particular class of compounds, its central theme is a fundamental reaction type, nucleophilic addition to carbonyl groups. The principles of nucleophilic addition to alde- hydes and ketones developed here will be seen to have broad applicability in later chap- ters when transformations of various derivatives of carboxylic acids are discussed. 17.1 NOMENCLATURE O X The longest continuous chain that contains the ±CH group provides the base name for aldehydes. The -e ending of the corresponding alkane name is replaced by -al, and sub- stituents are specified in the usual way. It is not necessary to specify the location of O X the ±CH group in the name, since the chain must be numbered by starting with this group as C-1. The suffix -dial is added to the appropriate alkane name when the com- pound contains two aldehyde functions.* * The -e ending of an alkane name is dropped before a suffix beginning with a vowel (-al) and retained be- fore one beginning with a consonant (-dial). 654 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website 17.1 Nomenclature 655 CH3 O O O O CH3CCH2CH2CH CH2 CHCH2CH2CH2CH HCCHCH CH3 4,4-Dimethylpentanal 5-Hexenal 2-Phenylpropanedial When a formyl group (±CHœO) is attached to a ring, the ring name is followed by the suffix -carbaldehyde.
    [Show full text]
  • Semicarbazone – a Versatile Therapeutic Pharmacophore for Fragment Based Anticonvulsant Drug Design
    Acta Pharm. 62 (2012) 263–286 Review DOI: 10.2478/v10007-012-0030-1 Semicarbazone – a versatile therapeutic pharmacophore for fragment based anticonvulsant drug design SURENDRA NATH PANDEYA During the last fifteen years, semicarbazones have been extensively investigated for their anticonvulsant proper- Department of Pharmacy, Saroj Institute ties. 4-(4-Flurophenoxy) benzaldehyde semicarbazone of Technology and Management Ahimamau (C0102862, V102862) was discovered as a lead molecule Lucknow-226002 (U.P.), India and is being developed as a potent antiepileptic drug, with maximal electroshock (MES) ED50 of i.p. 12.9 mg kg-1. In MES (oral screen), this compound has a protec- tive index (PI = TD50/ED50 > 315) higher than carbama- zepine (PI 101), phenytoin (PI > 21.6) and valproate (PI 2.17). The compound is a potent sodium channel blocker. Other semicarbazones have demonstrated activity in va- rious chemoshock screens, like subcutaneous pentylene- tetrazole, subcutaneous strychnine, subcutaneous picro- toxin and subcutaneous bicculine. Semicarbazones are also GABA-transaminase inhibitors. Extensive structure- -activity relationship has demonstrated that F, Cl, Br and NO2 substituents in the arylhydrophobic pocket and a hydrogen bonding domain (HBD) are generally found in active anticonvulsant agents. Keywords: semicarbazone, anticonvulsant, Na+ channel Accepted July 17, 2012 blocker Epilepsy is a brain disorder that causes people to have recurring seizures. Epilepsy affects 50 million people worldwide, and 50 % of them live in the developing world (1, 2). Many options are available, from different chemical classes such as hydantoins (3) barbiturates (4), benzodiazepines (5), gamma-aminobutyric acid (GABA) analogs (6), di- benzepines (7) and carbamates (8). All of these compounds are used in the treatment of epilepsy.
    [Show full text]
  • Hydration of Ketones and Aldehydes
    Hydration of Ketones and Aldehydes H H H O O H H H H HO OH H2O O O HO OH O a hydrated ketone H H O HO OH H2O Keq = 2000 uncrowded H H H H Aldehydes exist as partial hydrates in aqueous solution: O HO OH H2O Keq = 1 more crowded Me H Me H O H O HO OH Ketones generally do not favor hydration: 2 Keq = 0.002 very crowded Me Me Me Me Nucleophilic Addition of "O–" to Carbonyl Groups Na O O OH H+ (workup) O HO Na + H2O Me Me Me Me Me Me OH OH Me Me A hydrated ketone Starting material! pKa of H2O: approx. 16 pKa of alkoxide: 16-20 Na O O OH H+ (workup) O MeO Na + MeOH Me Me Me Me Me Me OMe OMe Me Me A hemiacetal Starting material! (usually unstable) pKa of MeOH: approx. 15 pKa of alkoxide: 16-20 Hydration of Ketones and Aldehydes 18 O 18 O H2 O + Me Me H cat. Me Me H H H 18O 18O H H H Me Me H H Me 18 18 O O H O OH O H H Me 18O Me Me H H H18O OH H Me Me 18 H O a hydrated ketone Me Me H 18 H O OH2 18 O 18O Me Me Me Me Addition of Alcohols to Carbonyl Groups: Acetal Formation O ROH, H+ RO OR Me Me Me Me An acetal MeOH H+ Me Me H H Me O O MeO OH H+ Me MeOHMe Me MeO OH MeOH Me Me a hemiacetal MeO OMe H Me Me Me MeO OH2 Me Me MeO OMe O Me Me Me An acetal Me MeOH H2O Acetals as Carbonyl Protecting Groups O OH MeMgCl Me Me Me Me Me MeO OMe MeMgCl No reaction Me Me O Br O Li–Bu O P(Ph)3 Br (Ph)3P X (Ph)3P Me Me Me Butyllithium will react with the ketone, and the reagent will react with itself! O MeO OMe MeOH, H+ MeO OMe (Ph) P Br Br 3 Me Me Me A stable reagent O O MeO OMe + H2O, H Me Me Cyclic Hemiacetals MeOH H+ Me H Me MeOH Me H MeO OH O O MeO OH Me
    [Show full text]
  • United States Patent (19) (11) 3,886,211 Keenan (45) May 27, 1975
    United States Patent (19) (11) 3,886,211 Keenan (45) May 27, 1975 54). CARBOXYLIC ACID HYDRAZIDE 57) ABSTRACT DERVATIVES Hydrazides containing, as a characterising feature, the 75) Inventor: John Francis Edmund Keenan, grouping having the formula: Cheadle Hulme, England (73) Assignee: Ciba-Geigy Corporation, Ardsley, R - CO.NH.N - C N.Y. (22 Filed: Mar. 5, 1970 (21) Appl. No.: 16,971 wherein R is alkyl, aryl or the group Related U.S. Application Data R 63 Continuation-in-part of Ser. No. 881,282, Dec. 1, t 1969, abandoned. c = N.NH (corn - 30 Foreign Application Priority Data R2 Dec. 10, 1968 United Kingdom............... 58503/68 wherein R is hydrogen or alkyl, R is alkyl or the 52 U.S. Cl..... 260/561 H; 252/5.5 A, 260/347.3; group -CH=N.NHCOR or R and R, together are cy 260/404.5; 260/482 R; 260/500.5; 260/554; cloalkyl or 5-nitrofuryl, R is alkylene, or a vinylene or 26O1558 H phenylene residue and n is 0 or 1; and synthetic lubri (51) Int. Cl........................................... C07 c 103/30 cant compositions comprising hydrazides having the 58 Field of Search...................... 260/404.5, 561 H formula: R 56 References Cited UNITED STATES PATENTS 2,355,911 8/1944 Graenacher ................. 2601404.5 X R2 3,182,039 5/1965 Remy............... ..., 260/561 H X 3441,606 4/1969 Moore et al........................ 260/56 wherein R is amino, alkyl, aryl or one of the group 3,547,646 12/1970 Hori et al........................ 260/56 H ings 3,564.048 2/1971 Fletcher et al.....................
    [Show full text]
  • 4,5-Dimethylphenol from 2-Hydroxy-4
    J. Chem. Sci. Ó (2020) 132:88 Indian Academy of Sciences https://doi.org/10.1007/s12039-020-01802-4Sadhana(0123456789().,-volV)FT3](0123456789().,-volV) REGULAR ARTICLE Synthesis and characterization of (E)-2-(1-hydrazonoethyl)-4, 5-dimethylphenol from 2-hydroxy-4,5-dimethylacetophenone DINKAR GAGAREa,* , RAJU PATILb, RAMA LOKHANDEa, POONAM DWIVEDIa and AJAY DESHMUKHa aJaipur National University, Jagatpura, Jaipur 302 017, India bInstitute of Science, Mantralaya, Fort, Mumbai 400 032, India E-mail: [email protected] MS received 18 March 2020; revised 5 May 2020; accepted 7 May 2020 Abstract. This study reports the development of a novel substituted hydrazone prepared from 2-hydroxy- 4,5-dimethylacetophenone and hydrazine in alkaline medium at controlled conditions which yields as cor- responding hydrazone [(E)-2-(1-hydrazonoethyl)-4,5-dimethylphenol]. The structure of synthesized (E)-2-(1- hydrazonoethyl)-4,5-dimethylphenol was elucidated by elemental analysis and spectroscopic techniques like infrared spectroscopy, ultraviolet–visible spectroscopy, high-performance liquid chromatography, proton nuclear magnetic resonance and mass spectrum. Keywords. 2-Hydroxy-4,5-dimethylacetophenone; hydrazone; hydrazine. 1. Introduction nucleophilic although the amino type nitrogen is more reactive. Due to the electrophilic and nucleophilic Hydrazone is the product of hydrazine with simple or properties, hydrazones are widely used in organic substituted acetophenone obtained in the alkaline synthesis.1,12 medium. Hydrazones are a class of organic compounds The hydrazones show a wide range of pharmaceu- 1 1,3,13 which possess the general structure R1R2C=NNH2. tical activities, such as antimalarial, antibacte- Hydrazones are aromatic in nature and shows that one rial,14–16 antidepressant,16 analgesic agents,17,18 aromatic ring linked with a hydrazine group.
    [Show full text]
  • Rpt POL-TOXIC AIR POLLUTANTS 98 BY
    SWCAA TOXIC AIR POLLUTANTS '98 by CAS ASIL TAP SQER CAS No HAP POLLUTANT NAME HAP CAT 24hr ug/m3 Ann ug/m3 Class lbs/yr lbs/hr none17 BN 1750 0.20 ALUMINUM compounds none0.00023 AY None None ARSENIC compounds (E649418) ARSENIC COMPOUNDS none0.12 AY 20 None BENZENE, TOLUENE, ETHYLBENZENE, XYLENES BENZENE none0.12 AY 20 None BTEX BENZENE none0.000083 AY None None CHROMIUM (VI) compounds CHROMIUM COMPOUN none0.000083 AY None None CHROMIUM compounds (E649962) CHROMIUM COMPOUN none0.0016 AY 0.5 None COKE OVEN COMPOUNDS (E649830) - CAA 112B COKE OVEN EMISSIONS none3.3 BN 175 0.02 COPPER compounds none0.67 BN 175 0.02 COTTON DUST (raw) none17 BY 1,750 0.20 CYANIDE compounds CYANIDE COMPOUNDS none33 BN 5,250 0.60 FIBROUS GLASS DUST none33 BY 5,250 0.60 FINE MINERAL FIBERS FINE MINERAL FIBERS none8.3 BN 175 0.20 FLUORIDES, as F, containing fluoride, NOS none0.00000003 AY None None FURANS, NITRO- DIOXINS/FURANS none5900 BY 43,748 5.0 HEXANE, other isomers none3.3 BN 175 0.02 IRON SALTS, soluble as Fe none00 AN None None ISOPROPYL OILS none0.5 AY None None LEAD compounds (E650002) LEAD COMPOUNDS none0.4 BY 175 0.02 MANGANESE compounds (E650010) MANGANESE COMPOU none0.33 BY 175 0.02 MERCURY compounds (E650028) MERCURY COMPOUND none33 BY 5,250 0.60 MINERAL FIBERS ((fine), incl glass, glass wool, rock wool, slag w FINE MINERAL FIBERS none0.0021 AY 0.5 None NICKEL 59 (NY059280) NICKEL COMPOUNDS none0.0021 AY 0.5 None NICKEL compounds (E650036) NICKEL COMPOUNDS none0.00000003 AY None None NITROFURANS (nitrofurans furazolidone) DIOXINS/FURANS none0.0013
    [Show full text]
  • Synthesis and Antibacterial Evaluation of Some Novel Hesperidin Semisynthetic Derivatives
    Available online a t www.scholarsresearchlibrary.com Scholars Research Library Der Pharmacia Lettre, 2014, 6 (1):87-94 (http://scholarsresearchlibrary.com/archive.html) ISSN 0975-5071 USA CODEN: DPLEB4 Synthesis and antibacterial evaluation of some novel hesperidin semisynthetic derivatives N. Duganath *1 , C. Sridhar 2 and K. N. Jayaveera 3 1Department of Pharmaceutical Chemistry, JNTUA Oil Technological Research Institute, Ananthapuramu, AP, India 2Sri Padmavathi School of Pharmacy, Tiruchanoor, Tirupathi, India 3Department of Chemistry, JNTUA College of Engineering, Ananthapuramu, AP, India _____________________________________________________________________________________________ ABSTRACT Flavonoids are one of the active principles isolated from plant sources. These compounds have found to have enormous pharmacological activity, Hesperidin, a molecule with a wide spectrum of pharmacological activity still has not been used for treatment of any diseases due to its lacking potency. The present study was focused to synthesize various derivatives of Hesperidin and to evaluate their activity. Among the various synthesized compounds, compound Hg, Hn and Hj have shown more potent activity even when compared with the compound. Whereas all other compounds were not potent as standard compound but were found to have increased in potency while comparing with the standard compound. Thus we conclude substitution of the oxygen moiety with the hydrazide to form hydrazones increases the antibacterial activity and presence of electron donating groups further increases the activity. Keywords : Hydrazone derivatives, Hesperidine, Ampicillin, Antibacterial activity. _____________________________________________________________________________________________ INTRODUCTION The flavonoids are one of the active principles isolated from plant sources. These compounds have found to have enormous pharmacological activity. Even though these compounds possess pharmacological activity still no remarkable molecule has come out of these molecules.
    [Show full text]
  • Facile Regeneration of Carbonyl Compounds from 2,4Dinitrophenylhydrazones, Oxime, Hydrazones, and Semicarbazones
    id5116234 pdfMachine by Broadgun Software - a great PDF writer! - a great PDF creator! - http://www.pdfmachine.com http://www.broadgun.com OOrrggaanniicc ISSN: 0974 - 7516 Volume 8 Issue 5 CCHHEEMMAn IIInSSdiTTan RRJouYrYnal Trade Science Inc. Short Communication OCAIJ, 8(5), 2012 [161-163] Facile regeneration of carbonyl compounds from 2,4dinitrophenylhydrazones, oxime, hydrazones, and semicarbazones Dinanath D.Patil*, Dnyandeo K.Mhaske, Gurumeet C.Wadhawa, Arun K.Deshmukh Department of Chemistry, R.B.N.B. College Shrirampur, Dist.: - Ahmednagar, (INDIA) E-mail: [email protected] Received: 16th August, 2011 ; Accepted: 16th September, 2011 ABSTRACT KEYWORDS Derivatives of carbonyl compounds such as oximes, phenylhydrazones, Protection; semicarbazones and thiosemicarba-zones are used not only for the charac- Aldehyde; terization and purification of carbonyl compounds[1,2] but also play an im- Ketone; portant role in the protection carbonyl compounds, as they are highly crys- Hydrazine hydrochloride; talline and stable compounds. Thus, the regeneration of carbonyl com- Sodium acetate. pounds from their derivatives under mild condition is important process in organic synthetic chemistry. We report classical method for the cleavage of oximes, phenylhydrazones, semicarbazones and thiosemicarbazones alde- hydes and ketones. 2012 Trade Science Inc. - INDIA INTRODUCTION pared reagents[6,7], tedious work-up, or they are often hazardous[3-6]. Although some of the known methods are 2,4-Dinitrophenylhydrazones and other derivatives carried out under mild reaction conditions,most of them of carbonyl compounds such oximes, phenylhy- require drastic conditions, high temperature, long reac- drazones[1,2], semicarbazones and thiosemicarbazones as tion times, toxic or not- readily available reagents,they are important Intermediates[3] in organic synthesis be- need to be freshly prepared, and have tedious work-up cause of their use in the characterization and purification- procedures.
    [Show full text]
  • Novel Semicarbazone-Based Amidoalkylation Reagents: Preparation and Application to the Stereoselective Synthesis of 14-Membered Hexaaza Macrocycles
    Novel Semicarbazone-Based Amidoalkylation Reagents: Preparation and Application to the Stereoselective Synthesis of 14-Membered Hexaaza Macrocycles Anastasia A. Fesenko, Alexander N. Yankov, Anatoly D. Shutalev* Moscow Technological University, 86 Vernadsky Ave., 119571 Moscow, Russian Federation Abstract An efficient general synthesis of hydrazones of 4-(3-oxobutyl)semicarbazones using novel semicarbazone-based amidoalkylation reagents has been developed. The prepared hydrazones were converted under acidic conditions into 14-membered cyclic bis-semicarbazones, 1,2,4,8,9,11- hexaazacyclotetradeca-7,14-diene-3,10-diones. Plausible pathway and stereochemistry of the macrocyclization are discussed. Keywords Semicarbazones; 4-(Tosylmethyl)semicarbazones; Hydrazones; Azamacrocycles; Amidoalkylation; retro-Claisen reaction; Heterocyclization Introduction Polyaza macrocycles are of considerable importance in various fields of chemistry, biochemistry, medicine, and material science. The unique features of these heterocycles arise from their ability to bind to different inorganic and organic cations, anions, and neutral molecules.1,2 Polyaza macrocycles and their metal complexes possess a wide range of biological activities3 including anticancer,4 anti- HIV,5 antibacterial and antifungal properties.6 The metal complexes also have applications as contrast agents for magnetic resonance imaging,7 radiopharmaceuticals,8 sensors,9 NMR shift reagents,10 luminescent materials,9c,10b and catalysis.2d,11 Although a large variety of polyaza macrocycles have been synthesized, the design of new members, particularly tetradentate 14-membered hexaazacycles, is a topic of great interest. Among them, 14-membered 1,2,4,8,9,11-hexaaza macrocycles remain underexploited.12 Recently, we reported a general approach to novel 14-membered cyclic bis-semicarbazones 1 based on the acid-catalyzed cyclization of 4-(3-oxobutyl)semicarbazide hydrazones 2 (Scheme 1).13 Scheme 1.
    [Show full text]
  • Synthesis of Some Novel Semicarbazone and Thiosemicarbazone Derivatives of Isatin As Possible Biologically Active Agents
    Journal of Pharmaceutical Research International 17(6): 1-13, 2017; Article no.JPRI.35243 Previously known as British Journal of Pharmaceutical Research ISSN: 2231-2919, NLM ID: 101631759 Synthesis of Some Novel Semicarbazone and Thiosemicarbazone Derivatives of Isatin as Possible Biologically Active Agents Masoumeh Divar 1,2 , Ali Khalafi-Nezhad 2, Kamiar Zomorodian 3, Razieh Sabet 4, Zahra Faghih 5, Maryam Jamali 4, Hasti Pournaghz 4 and Soghra Khabnadideh 1* 1Faculty of Pharmacy, Pharmaceutical Sciences Research Center, Shiraz University of Medical Sciences, Shiraz, Iran. 2Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran. 3Basic Sciences in Infectious Diseases Research Center, School of Medicine, Shiraz University of Medical Sciences, Shiraz, Iran. 4Faculty of Pharmacy, International Branch, Shiraz University of Medical Sciences, Shiraz, Iran. 5Cancer Immunology Group, Shiraz Institute for Cancer Research, Medical School, Shiraz University of Medical Sciences, Shiraz, Iran. Authors’ contributions This work was carried out in collaboration between all authors. Authors MD and AKN designed, synthesized and analyzed the data of the Isatin derivatives. Authors KZ, RS, ZF, MJ, HP and SK prepared the antimicrobial and cytotoxicity tests. Authors MD and SK wrote the paper. All authors read and approved the final manuscript. Article Information DOI: 10.9734/JPRI/2017/35243 Editor(s): (1) Syed A. A. Rizvi, Department of Pharmaceutical Sciences, College of Pharmacy, Nova Southeastern University, USA. Reviewers: (1) Prakashanand Caumul, University of Mauritius, Mauritius. (2) Ahmed Mohammed Abu-Dief Mohammed, Sohag University, Egypt. (3) Chong Leong, Gan, Universiti Malaysia Perlis, Malaysia. Complete Peer review History: http://www.sciencedomain.org/review-history/20102 Received 1st July 2017 th Original Research Article Accepted 14 July 2017 Published 18 th July 2017 ABSTRACT Aims: The development of new beneficial agents is one of the crucial aims in medicinal chemistry.
    [Show full text]
  • Synthesis and Antibacterial Studies of Some Semicarbazones of Some Carbonyl Compounds
    International Journal of Science and Research (IJSR) ISSN (Online): 2319-7064 Index Copernicus Value (2013): 6.14 | Impact Factor (2013): 4.438 Synthesis and Antibacterial Studies of Some Semicarbazones of Some Carbonyl Compounds S. B. Singh1, Ashok Kumar2, Galal M Zaiad3, Amit Chattree4 1, 4 Department of Chemistry, Sam Higginbottom Institute of Agriculture, Technology and Sciences, Allahabad, U.P., India 2, 3 Department of Chemistry, Faculty of Sciences, Al-mergheb University, Al-Khoms, Libya Abstract: A number of semicarbazone derivatives were synthesized by the condensation reaction of appropriate ketones with semicarbazide and all the compounds were characterized by analytical and spectral studies. The compounds were evaluated for their antibacterial activity against pathogenic bacteria by using agar well diffusion method. Most of the compounds were found to have better antibacterial action than the reference standard drugs. Keywords: Synthesis, condensation reaction, semicarbazones, antibacterial activity, agar well diffusion method H C O O 1. Introduction 3 H3C MeOH\ Glacial acetic acid O H N NH NH + 2 2 N NH NH2 Semicarbazones [general structure : RC=NNHC(=O)NH2] H3C H C are formed by the condensation of aldehydes or ketones with 3 Ketone Simecarbazide semicarbazide [NH2NHC(=O)NH2] [1] and have been Simecarbazone Scheme-1 evaluated for various biological activities including anticonvulsant [2] [3], analgesic and anti-inflammatory [4], Synthesis of acetophenone semicarbazone (SCz 1) : antitubercular [5],antifungal and antibacterial [6][7], Acetophenone (10 ml, 0.056 mol) was taken in a round anticancer [8][9] etc. These medicinal properties of bottom flask and 10 ml semicarbazide was added and 10 ml semicarbazones developed an interest among medicinal methanol solution with 10 ml glacial acetic acid and heated chemists and biologists to undertake their preparation and in a distillation unit, then synthesized compound was dried evaluate their biological properties to investgate better and collected.
    [Show full text]