DOCSLIB.ORG

Oxidation Ofsemicarbazide, Thiosemi- Carbazide, Carbohydrazide

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Oxidation Ofsemicarbazide, Thiosemi- Carbazide, Carbohydrazide - c ~ .., Indian Journal of Chemistry Yol. 32A. October 1993, pp. 921-924 Oxidation of semicarbazide, thiosemi• Experimental carbazide, carbohydrazide, thiocarbo• Cobalt(III) solution was prepared by the anodic hydrazide, thiocyanate, thiourea and oxidation in a divided electrolytic cell consisting their derivatives with aquocobaltic of platinum electrodes. The anolyte consisted of ions in acid media 200 cm3 of cobaltous nitrate in HN03 (1.0 mol dm-3) or cobalt(ll) sulphate in H2S04 (3.0 mol dm-3') or cobalt(ll) perchlorate in HCI04 (3.0 S D Ravi Prakash t, B S Sherigara* & A M Abdul Khader mol dm - 3). The catholyte was the corresponding Department of Chemistry, Mangalore University, acid solution of appropriate concentration. The Mangalagangotri 574199, India temperature (5°C) was controlled by an ice bath. Received 8 December 1992; revised and accepted The electrolysis was carried out at a cell voltage 10 February 1993 of 6V and anodic current density of 2 miDi amps Conditions have been verified for the electrogenera• cm - 2. The concentration of Co(III) generated was tion of Co(ill) from Co(ll) in aqueous nitric acid, sul• determined by adding an aliquot to an excess of phuric acid and perchIoric acid. The Co(ill) species KI solution and titrating the liberated iodine with formed have been identified and characterised. The a standard thiosulphate solution. The value was stability of a standard solution of Co(ill) has been further checked by adding excess of standard ir• studied and conditions for the volumetric determina• on(ll) solution to an aliquot of the electrolysed tion of the probable number of electrons involved in solution and titrating the excess Fe(ll) with Cr(Vl) the oxidation of certain classes of compounds by solution using barium diphenylamine sulphonate Co(ill) in different acids, have been investigated. Oxi• as an internal indicator. The UV-visible spectrum dation products have been identified and the stoichio• of the species in 1 mol dm-3 HN03 medium metries established. The number of electrons involved showed two peaks at 600 nm and 400 nm with in these redox reactions are dependent on the nature of the reductant molecules and the reaction condi• molar absorptivity of about 40, corresponding to tions. the expected electronic transitions. Semicarbazide hydrochloride and thiosemicarb• azide(TSC) (Loba-Chemie, India) were used after In previous years considerable amount of work recrystallisation, Semicarbazones of aldehydes, on kinetics of redox reactions of Co(III) species benzaldehyde, 4-chlorobenzaldehyde, 4-nitroben• has been carried out and it has been reviewed by zaldehyde, salicylaldehyde and benzaldehyde thio• Davies and Wamqvistl and Waters and Littler2. semicarbazone and the metal comple'i,es, The instability of cobalt(III) solution involving M(TSChSO 4 (M = Ni2+ , Zn2+ or Cd2+) were pre• pared by the literature method7,8. Thiocarbo• Co;; or CoO~~ is the major hurdle in its use as an oxidising agent. However, at moderately high hydrazide (TCH), zinc thiocarbohydrazide com• aCidities and at temperature nearer zero degree plex, Zn(TCHhCl2, and carbohydrazide were pre• pared by the methods described elsewhere9• celsius, Co~~ can be obtained in a stable form and can be used in redoximetric studies. Back titration method As a part of the kinetic and analytical investig• cm3) ations of metal ion oxidations3-6, we report herein, To a known volume (VI of the reductant Co(llI) oxidation of semicarbazide, thiosemicarba• (5.0 cm3 of 0.001 mol dm-3, in a medium of 3.0 mol dm - 3 of the acid) was added a known excess zide, their derivatives, their higher homologues, of the oxidant (25.0 cm3 of 0.002 mol dm3) and namely, carbohydrazide, thiocarbohydrazide and the reaction mixture was allowed to stand for dif• certain other reductants like thiocyanate and thi• ferent intervals of time to ascertain the comple• ourea, by cobaltic ions in nitric, sulphuric and tion of the reaction, in a water bath maintained at perchloric acid media. Because of the synthetic importance of these compounds their oxidation 5 ± 2°C, with occasional shaking. Excess oxidant' reactions might be important. was determined by reacting with an equivalent amount of potassium iodide and then titrating with standard sodium thiosulphate solutiQIl to the 'Present address: Nehru Memorial College, Sullia, Karnataka. starch end point (the titre, V2 cm3). A blank titra- 922 INDIAN J OHEM, SEe. A, OCTOBER 1993 Semicarbazones in H2S04 and HN03 medium . same ali uot volume of Co(III) under id ntical reacted in two stages, namely two electron oxida• , conditio s (the titre V3 cm3). The number f elec• tion of the semicarbazones with the regeneration tronstion was]perfOrmedinv lved in the reactionsimultaneouslyis given by Eq.tak]'(1)g the of the respective aldehydes and two electron oxi• dation of the aldehyde to corresponding carbo• xylic acid. Here again in .. (1) C6HsCH = N - NH - CO - NH2 + H20 + 2C03+ • C6HsCHO + HN = N - CO - NH1 + 2C02 + + 2H+ wherethiosulph~tex landandyarethe reductantthe molaritiesrespectivelyof the. sbdium ... (4, C6HsCHO + 2C03 + + H20 - C6HsCOOH + 2Co2+ + 2H+ ... (5) ~ ous HN 3' H2S04 and HCI04 contains C ;q+ or • Co(OH);. as reactive specieslO• The pu lished perchlonc acid medium, the first stage of the reaction involved 4 electrons. The second stage of value]]ResultsIt has fIdreenthediscussionestablishedequilibriumthatconstantcobalt(III),(Kh) in~aque•f the reaction, reaction i.e. oxidation of aldehyde to carboxylic acid was relatively slow in all the three acid media Kh and the whole titration took 45-60 min. The alde• 20 <= CoO~q~ + H+ hyde formed could be identified in the initial stages of the reaction, by its 2,4-dinitrophenyl hy• drazone derivative in all the three acid media. Oxidation of TSC and its derivatives by aquo redox po ential (EO) of CO;q+/CO;q+ couple n non cobaltic ions was drastic and yielded reproducible I complexi g aqueous solutions like nitric a id or 6 electron stoichiometry in all the three media ~. perchlori acid media has been reporte 11 as is1.86(2 ± Q.1) 21O-3.molV versus dm-3standardat 25°C.hydrogenThe elest~dardtrode (Eq.6) at, [H+f 3.0 mol dm-3. \ H2N - NH - CS-NH2 + 6C03 + 5H20 - Co(III) solutions (1-3.0 x 10 - 3 mol dm - ) pre• + pared by the anodic oxidation of Co(II) s lution CNO- + 2NHt + SO~- + 7H+ + 6Co2+ ... (6) at low c rent density ( - 2 mA cm - 2), at oder• ately hig acidity (1-3 mol dm - 3) and at n op• NHt and SO~- were identified as the products erating t mperature, below 5°C, were mod rately by Nesler's test and BaCl2 reaction (in nitric and stable wi h less than 2% deterioration per 12 h. perchloric acid media) respectively. An attempt to The sta lity of the solution in different media detect CNO~ was not successful, probably be• were fou d by monitoring the changes in c ncen• cause free cyanic acid (HCNO) which was liberat• i'i'1',· tration w th time by iodometric method. Th stab• ed initially was decomposed into CO2 and NH3 iUties of e solutions were in the order: nit 'c ac• and the latter combined with the H2S04 present - t i " id > sulp uric acid> perchloric acid. to form ammonium sulphate. A little of the cyanic ~ acid, however, was not decomposed and was re• I The st istical data obtained from these r~doxi• cognised in the evolved gas by its penetrating metric s ies are presented in Table 1. odour. ,t'1 , In case of benzaldehyde thiosemicarbazone, the mediumSemica nderwentbazide in twonitricelectronacid andchangesulphuri~oxitlationacid ,I reaction proceeded in two stages by the regenera• by Co(III as with Mn(III)12,13. tion of benzaldehyde and further oxidation of benzaldehyde to benzoic acid. H2NH2N- c<p-lco-N=NH+2C02+- NH - NH2 + 2C03+ +• 2H+ ... (2) Titrations with an aqueous solution of the metal complex, M(TSC}zS04' where M=NF+, Zn2+ or Cd2+ were very convincing, as twelve electron . But in p rchloric acid medium, the reaction In• volved fo r electrons as shown by Eq. (3) stoichiometry conformed to two TSC ligand molecules being present in the complexes as fol• H2N-C -NH-NH2+4Co3+ +H20- lows: M(H2N - HN -CS- NH2)2S04 + 12C03++ lOHzO• NHtCO2 + wN +identifiedNHt + 4C02in +the+ 3Hreaction+ mix~ref .. (3)by 12Co2+ + 3S0~- + 4NHt + 2CNO- + 14H+ + M2+ Nessler's est. ... (7) I l!i .1""" 'I' " """ L." 11.11 11!illll,1 1111".11111.111 'Iitil NOTES 923 4.1 ±0.02 p-ChlorobenzaldehydeBenzaldehydeSalicylaldehydem-Nitrom-Nitrobenzaldehydep-ChlorobenzaldehydeSalicylaldehydeNi(TSChS04Zn(TCHhCI2Zn(TSChS04ThiocarbohydrazideThiosemicarbazideCd(TSChS04CarbohydrazideBenzaldehydeRJtassiurnbenzaldehyde15Tablethiocyanatesemicarbazone5,89±0.025.91thiosernicarbazoneH2SO42.046.0712.09±0.062.08(35.9212.083.94±0.0311.9712.04±0.021.953.076.05HCI041.963.893.97±0.032.053.961.937.915.963.0611.93±0.0211.948.115.9511.93semicarbazone4.13.9I-Volumetricmolmoldm-3)±O.o1(TSC)±O.ot±±0.02±O,02±0.03±O.o1±0,02±0.01±0.02±0.04(TCH)±0.02±O.ot±0.01±O.o1dm-3)0.01semicarbazone0.01semicarbazone(0.11-0.45)determination12.06±0.0212.0411.9411.916.060.807,882.033,933.965,943,951.961.953.91Number-2.94±0.02±±0.04±O.o1±0.Q1±0.02±0.03±0.01±O,O1± 0.020.060.01of probableof electronnumberparticipatingof electronsin involvedredox reaction"in the oxidation± SDb of certain compounds by "\, , 11(0.08-0.33) >. (1 mol dm-3) ~ Co(lIl)in acid media at 5 ± 2°C (0.28-1.67)(0.26-1.06(0.35-1.40(0.52-2.08)(0,37-1.51(0.49-1.97)((0.11-0.44(0.40-1.63)(0.30-1.22)(0.02-0.76)(0.02-0.09)(0.02-0.10)(0.44-1.79)Sernicarbazide(0.09-0.34)(0.09-0.39)(0.08-0.34))) (range19' ThioureastudiedCompoundin mg) 1810161413171289645237 (0.96<UnderbStandard± 0.02)<reductantdeviationexcessfor fivecondition-excessdeterminations.
Load more

Recommended publications
  • WO 2012/044761 Al
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date _ . 5 April 2012 (05.04.2012) WO 2012/044761 Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every A61K 47/48 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) International Application Number: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US201 1/053876 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 29 September 201 1 (29.09.201 1) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (25) Filing Language: English NO, NZ, OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, (26) Publication Langi English RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, (30) Priority Data: ZM, ZW. 12/893,344 29 September 2010 (29.09.2010) US (84) Designated States (unless otherwise indicated, for every (71) Applicant (for all designated States except US): UNI¬ kind of regional protection available): ARIPO (BW, GH, VERSITY OF NORTH CAROLINA AT WILMING¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, TON [US/US]; 601 South College Road, Wilmington, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, NC 28403 (US).
    [Show full text]
  • 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]
  • 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.
    [Show full text]
  • United States Patent Office Patented Mar
    3,171,249 United States Patent Office Patented Mar. 2, 1965 i 2 fuel rocket engine. The above and other objects of this 3,171,249 PROPELLANT AND Rick |PROPULSSON METH invention will become apparent from the discussion OXD EMPLOYANG EYERAZINE WITH AMSNO which follows. TETRAZOLES The objects of this invention are accomplished by the Ronald E. Be, Canoga Park, Calif., assigner to use of compounds having the general formula: North American Aviatiosa, Bac. No Drawing. Fied Nov. 29, 1961, Ser. No. 155,803 NH2. (R) 8 Clains. (C. 60-35.4) N This invention relates to a novel rocket propellant. YS More particularly, this invention relates to a novel in 10 N--H proved rocket propellant and a method of operating a wherein x varies from 0 to 1 and R is selected from the rocket engine. class consisting of HCl, H2O, HNO3, and HCIO, as addi The criterion by which rocket propellants are classi tives to a hydrazine-based rocket fuel in an amount suffi fied is specific impulse, Is, defined as thrust in pounds 5 cient to depress the freezing point at least 40° C. while divided by the total mass flow of fuel and oxidizer in retaining about the same density impulse and specific pounds per second. Specific impulse is thus given in impulse. Hence, an embodiment of this invention com units of "seconds.” Oxidizer-fuel propulsion system prises a method of operating a rocket engine comprising compositions with a relatively high specific impulse are ejecting from the reaction chamber of the engine a gaseous known in the art.
    [Show full text]
  • Rozprawa Doktorska
    WOJSKOWA AKADEMIA TECHNICZNA im. Jarosława Dąbrowskiego WYDZIAŁ NOWYCH TECHNOLOGII I CHEMII ROZPRAWA DOKTORSKA Judyta REĆKO (imiona i nazwisko dyplomanta) Otrzymywanie i badanie koordynacyjnych związków wybuchowych zawierających 4,4’,5,5’-tetranitro-1H,1H’-2,2’- biimidazol (tytuł rozprawy doktorskiej) Nauki chemiczne, Chemia (dziedzina nauki, dyscyplina naukowa) prof. dr hab. inż. Stanisław CUDZIŁO (stopień wojskowy/naukowy, imię i nazwisko promotora pracy) WARSZAWA - 2020r Spis treści Wykaz stosowanych skrótów ................................................................................................. 4 Wprowadzenie ....................................................................................................................... 7 1. Związki koordynacyjne ...................................................................................................... 8 2. Koordynacyjne materiały wybuchowe ............................................................................ 10 2.1. Koordynacyjne materiały wybuchowe zawierające amoniak ....................................... 10 2.2.Koordynacyjne materiały wybuchowe zawierające hydrazynę ..................................... 11 2.3.Koordynacyjne materiały wybuchowe zawierające aminy alifatyczne ......................... 14 2.4. Koordynacyjne materiały wybuchowe zawierające karbohydrazyd ............................ 17 2.5. Koordynacyjne materiały wybuchowe z pochodnymi guanidyny ................................ 19 2.6. Koordynacyjne materiały wybuchowe zawierające imidazol .....................................
    [Show full text]
  • United States Patent Office Patented Aug
    3,461,106 United States Patent Office Patented Aug. 12, 1969 1. 2 have insufficient fastness, frequently accompanied by 3,461,106 PGLYURETHANE FBERS insufficient absorption rates and depth of colour of the Harald Oertel and Heinrich Rinke, Leverkusen, Wilhelm dyeings, factors which also have a negative effect on the Thoma, Cologne-Flittard, and Friedrich-Karl Rosen fastness of such dyeings to abrasion. Further, the over dahl, Leverkusen-Schlebusch, Germany, assignors to dyeing properties are in many cases inadequate owing Farbenfabriken Bayer Aktiengeseischaft, Leverkusen, to the poor wash fastness of the dyeings. If, however, Germany, a corporation of Germany polyurethane elastomer fibres are to be widely used No Drawing. Fied May 21, 1965, Ser. No. 457,800 for textile purposes, the obtaining of deep and fast dye Claims priority, application Germany, May 23, 1964, ings is essential. This applies especially to the use of F 42,970 important groups of dyes such as acid dyes, metal com int. C. C08g 22/04, 22/06 O plex dyes or chrome dyes with which fast dyeings in U.S. C. 260-75 11 Claims deep colour tones can be obtained e.g. on polyamides which are used preferentially in conjunction with elastic polyurethane threads. The stability of polyurethane ABSTRACT OF THE DISCLOSURE 5 elastomer threads and foils to discolouration in light and Segmented polyurethane elastomers having improved to yellowing under the effect of atmospheric waste gases dyeability containing a repeating unit and having at least (especially nitrous gases and waste gases of combustion) one carboxylic acid hydrazide grouping and at least one still leaves room for improvement.
    [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]
  • Annex XV Dossier PROPOSAL for IDENTIFICATION of a SUBSTANCE AS a CATEGORY 1A OR 1B CMR, PBT, Vpvb OR a SUBSTANCE of an EQUIVALEN
    ANNEX XV – IDENTIFICATION OF HYDRAZINE AS SVHC Annex XV dossier PROPOSAL FOR IDENTIFICATION OF A SUBSTANCE AS A CATEGORY 1A OR 1B CMR, PBT, vPvB OR A SUBSTANCE OF AN EQUIVALENT LEVEL OF CONCERN Substance Name(s): Hydrazine EC Number(s): 206-114-9 CAS Number(s): 302-01-2 Submitted by: European Chemical Agency on request of the European Commission Version: February 2011 PUBLIC VERSION: This report does not include the Confidential Annexes referred to in Part II. 1 ANNEX XV – IDENTIFICATION OF HYDRAZINE AS SVHC CONTENTS PROPOSAL FOR IDENTIFICATION OF A SUBSTANCE AS A CATEGORY 1A OR 1B CMR, PBT, VPVB OR A SUBSTANCE OF AN EQUIVALENT LEVEL OF CONCERN ................................................................................7 PART I..........................................................................................................................................................................8 JUSTIFICATION .........................................................................................................................................................8 1 IDENTITY OF THE SUBSTANCE AND PHYSICAL AND CHEMICAL PROPERTIES .................................8 1.1 Name and other identifiers of the substance...................................................................................................8 1.2 Composition of the substance.........................................................................................................................9 1.3 Physico-chemical properties...........................................................................................................................9
    [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]