DOCSLIB.ORG

Boron Trifluoride Complexes of Aromatic Aldehydes. V. the CHO :BF, Pseudosubstituentl

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Boron Trifluoride Complexes of Aromatic Aldehydes. V. the CHO :BF, Pseudosubstituentl 2724 Boron Trifluoride Complexes of Aromatic Aldehydes. V. The CHO :BF, Pseudosubstituentl Mordecai Rabinovitz* and Amiram Grinvald Contribution from the Department of Organic Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel. Received April 27, 1971 Abstract: Boron trifluoride forms solid, stable 1 : 1 u-u complexes with aromatic aldehydes. The CHO :BFa pseudosubstituent proved to be an extremely strong electron-withdrawing group. The ir, uv, and nmr spectra of 17 such complexes were correlated with a new data matrix technique and compared with NOz, CHO, and CHOH+ benzene derivatives. n 1878 Landolf reported the formation of solid com- correlated with the respective properties of the free I plexes when aromatic aldehydes are treated with aldehydes, the protonated aldehydes (bearing the boron trifluoride.2 Almost 80 years later, Lombard pseudosubstituent CHOH+), and the analogous nitro- and Stephan prepared a series of such complexes in benzene derivatives. The energy differences between an analogous manner and studied their thermal be- the ground- and excited-state levels of the complexes, havior., No attempt has been made to characterize their electron-withdrawing properties, and the nature these complexes and no structure was suggested. In of complexation have been determined. The large 1965, Mhyre and coworkers isolated a stable complex volume of data accumulated in the present study of boron trifluoride and mesitaldebde and studied prompted us to develop a new method for its rapid its ir and uv ~pectra.~The scarcity of information evaluation and for the correlation of our experimental regarding these interesting complexes prompted us results with other data taken from the literature (the to start a detailed study of these compounds with a data matrix); vide supra. view to establishing their structure and ground- and excited-state properties. We thought that if these Experimental Section complexes would prove to be of a 1:l composition, aldehyde :BF3 and the boron trifluoride directly linked Table I shows the uv spectral data of the 17 complexes and Table I1 shows some ground-state properties of these complexes in to the aldehyde function, the resulting group CHO: BF, methylene chloride solution. The complexes are sensitive to might be considered as a pseudosubstituent, e.g., Ia. humidity, and they have to be prepared and maintained under The formyl (CHO) substituent by itself is a strong elec- strict anhydrous conditions. All complexes except those derived tron-withdrawing group, and we expected that the from p-nitrobenzaldehyde and p-cyanobenzaldehyde can be pre- pared in a carbon tetrachloride solution of the aldehyde, by addi- CHO:BF, group would be a much stronger electron- tion of boron trifluoride etherate. All these complexes are pre- withdrawing group. Such a pseudosubstituent would cipitated by the addition of boron trifluoride gas to the free alde- stabilize resonance forms favoring a high carbon- hyde in carbon tetrachloride solution at room temperature. Reg- carbon n-bond character in the ground state, e.g., Ib. ular crystals are obtained from methylene chloride solutions satu- rated with the complexes. The complexes can be preserved for The first indication to this effect came from the nmr long periods of time. Some of them, especially those bearing an studies which demonstrated the relatively high bar- electron-donating substituent, could be kept as solids for over 1 rier to rotation about the Caryl-Cformylbond.6 We year in sealed ampoules. The only unstable complexes are the ones with an electron-withdrawing substituent. Some of the more H, H, @O:BF, stable complexes can be sublimed. Elementary analyses of the C complexes were within experimental error and all complexes gave I the ratio BFa/aldehyde = 1. Nmr spectra were recorded at high settings of amplitude, and the purity of the complexes at low tem- peratures (lower than their exchange temperatures) was shown to be >99%, and no free aldehyde could be detected. We assume, there- X x+ fore, that these are stable 1 : 1 boron trifluoride-aromatic aldehyde Q 0 complexes. The spectra of both the isolated complexes and of the Ia Ib complexes prepared in sifu (Le., by passing gaseous boron tri- fluoride through the solution) are identical, although in the latter report the ground- and excited-state properties and the there is an excess of boron trifluoride. nature of bonding of these complexes and their rela- The aromatic aldehydes were distilled twice in uucuo immediately before use. Methylene chloride of analytical grade was washed tion to the parent free benzaldehydes. with concentrated sulfuric acid, distilled into a flask containing cal- This Study. We have prepared 17 complexes of sub- cium hydride from which it was redistilled, and preserved with mag- stituted aromatic aldehydes and boron trifluoride and nesium perchlorate (Anhydrone). The uv spectra were determined determined their ultraviolet, infrared, and nmr spectra. in 1-cm pathway cells with the aid of a Unicam SP-800 spectro- The absorption bands and extinction coefficients were photometer. The extinction coefficients of the free aldehydes were determined at two or more concentrations, and the difference be- (1) Part IV: M. Rabinovitz and A. Grinvald, TetrahedronLett.,4325 tween the two determinations was no greater than f2x. The ex- (1971). tinction of the solution was determined before and after passage of (2) M. Landolf, C.R. Acad. Sci., 86, 671 (1878). gaseous boron trifluoride through the solution. Subsequently, a (3) R. Lombard and J. P. Stephan, Bull. SOC.Chim. Fr., 1369 (1957); third measurement was obtained, by the addition of 1 drop of dilute 1458 (1958); R. Lombard and J. P. Stephan, C. R. Acad. Sci. Paris, 239, ethanol, giving a spectrum which superimposed the original alde- 887 (1954). (4) P. C. Myhre, C. D. Fisher, A. T. Nielsen, and W. M. Schubert, hyde. Solutions of the precipitated complex always showed the J. Amer. Chem. SOC.,81, 29 (1965). superimposed spectra of both the complex and the aldehyde. (5) A. Grinvald and M. Rabinovitz, Chem. Commun., 642 (1969). Therefore, dilutions were made in methylene chloride saturated with Journal of the American Chemical Society 1 94:8 j April 19, 1972 2725 Table I. Spectral Data of Benzaldehydes and Their Boron Trifluoride Complexes r -B band . _____C band - -Aband-- -E----- -Amax, nmb- -- F Amax e Transitionenergy -A,,,, -A,,,, nmn- Com- Alde- Com- Alde- Com- Alde- Corn- Com- difference, AET Substituent Complex Aldehyde plexc hyded plex hyde plexe hyde plex plexe AET~ AET~ 282 1. 4-H 281.6 246.5 18,800 12,800 330. 1330 1240 -290s 14.5 14.8 294a 235 9,100 14.1 2411 17.1 3. 4-CH(CH& 298.0 258.4e 25,800 17;500 -2910 14.7 4. 4-CH3 285.7 251.2~ 18,300 12,400 339 295 3150 1850 13.7 12.6 2831 5. 4-F 285.3 249.0 16,900 12,600 800 14.6 2748 f 6. 4-C1 298.5 257.8 23,600 18,100 2901 1300 15.1 281. f 291O 7. 4-Br 307.0 262.0 24,000 19,300 -1700 16.0 2828 f 1900 13.3 11.3 8. 4-CN 251'5 31,100 :::Ef 3258 2918 284S 260.01 299' f -1600 1700f 9.5 8.5 9. 4-NOz 278.4 265 21,600 15,500 320' 304 -3000 2450 5.0 7.4 401 i 1 13.2 10. 4-N(CH& 338.Y 32,800 -265 i 389 =t If 10.8 12.6 268 343i 35,500 i 10.4 12. 3,5-CH3 294.5 256.4 18,400 12,300 342 299 1960 1670 14.4 12.0 13. 3,5-OCH3 320.0 269.9 10,800 7,600 391 325.5 2290 2750 237 17,500 16.6 14.7 14. 3,4,5-OCH, 368 + 1 287.5 17,600 12,100 -3178 234 16,300 21.8 15. 2,643 287.5k 252.6k 11,200 6,900 362 306 2940 1810 13.7 14.3 16. 2-OCH3 287.5 253.6 15,200 10,500 380 319 6020 4950 13.3 14.3 17. 2,4,6-CHa 305.4 265.7 24,800 14,400 347 299 3860 2160 14.0 13.2 i0.2 nm. * =tl nm. Superscript s denotes shoulder. c &5z. &2%. e =tlOz;.f Doublet. 0 Nonsymmetrical unresolved dou- blet. Nonsymmetrical peak probably due to an absorption at 305 nm. E <2500. j Nonsymmetrical probably due to an absorption at 310 nm. Nonsymmetrical toward higher wavelengths. Table n. Ground-State Properties of Benzaldehydes and Their BF3 Complexes -1r Nmr - Ionization --Yc,o, cm-l- d,cps- potential of Subst it uent Aldehyde Complex Av, cm-l Aldehyde Complex A& cps hC-H, cps aldehydea 1. 4-NO2 1712 1642 70 1017.8 999.9 17.6 179.3 10.27 2. 4-CN 1711 1642 69 1011.4 992.2 19.2 178.9 3. 2,6-C1 1711 1631 80 1048.3 1022.2 26.1 187.7 4. 3,5-OMe 1703.5 1622 81.5 988.5 956.9 31.6 175.5 5. 4-CI 1703.5 1627 76.5 1003.1 968.1 35 175.9 9.61 6. 4-Br 1703 1626 77 997.1 970.3 26.5 175.7 7. 4-H 1703 1626 77 998.4 970.5 21.9 174.2 9.73 8. 4-F 1702 1627 75 997.3 966.1 31.2 175.1 9. 4-i-Pr 1701.5 1625 76.5 993.4 957.8 35.6 173 10. 3,5-Me 1698 1624 74 989.9 956.2 33.7 172.9 11. 4-Me 1695 1619 76 992.1 955.7 36.4 173.1 9.33 12.
Load more

Recommended publications
  • Borontrifluoride Etherate Safety Data Sheet 6160301 According to Federal Register / Vol
    Borontrifluoride etherate Safety Data Sheet 6160301 according to Federal Register / Vol. 77, No. 58 / Monday, March 26, 2012 / Rules and Regulations Date of issue: 02/09/2016 Version: 1.0 SECTION 1: Identification 1.1. Identification Product form : Substance Substance name : Borontrifluoride etherate CAS No : 109-63-7 Product code : 6160-3-01 Formula : C4H10BF3O Synonyms : Boron trifluoride diethyl etherate Other means of identification : MFCD00013194 1.2. Relevant identified uses of the substance or mixture and uses advised against Use of the substance/mixture : Laboratory chemicals Manufacture of substances Scientific research and development 1.3. Details of the supplier of the safety data sheet SynQuest Laboratories, Inc. P.O. Box 309 Alachua, FL 32615 - United States of America T (386) 462-0788 - F (386) 462-7097 [email protected] - www.synquestlabs.com 1.4. Emergency telephone number Emergency number : (844) 523-4086 (3E Company - Account 10069) SECTION 2: Hazard(s) identification 2.1. Classification of the substance or mixture Classification (GHS-US) Flam. Liq. 3 H226 - Flammable liquid and vapour Acute Tox. 4 (Oral) H302 - Harmful if swallowed Acute Tox. 1 (Inhalation) H330 - Fatal if inhaled Skin Corr. 1A H314 - Causes severe skin burns and eye damage Eye Dam. 1 H318 - Causes serious eye damage STOT SE 3 H335 - May cause respiratory irritation STOT RE 1 H372 - Causes damage to organs through prolonged or repeated exposure Full text of H-phrases: see section 16 2.2. Label elements GHS-US labeling Hazard pictograms (GHS-US) : GHS02 GHS05 GHS06 GHS07 GHS08 Signal word (GHS-US) : Danger Hazard statements (GHS-US) : H226 - Flammable liquid and vapor H302 - Harmful if swallowed H314 - Causes severe skin burns and eye damage H330 - Fatal if inhaled H335 - May cause respiratory irritation H372 - Causes damage to organs through prolonged or repeated exposure Precautionary statements (GHS-US) : P210 - Keep away from heat/sparks/open flames/hot surfaces.
    [Show full text]
  • PATENT OFFICE PROPONCACD SYNTHESS Donald J
    Patented Aug. 29, 1939 2,170,825 UNITED STATES 2,170,825PATENT OFFICE PROPONCACD SYNTHESS Donald J. Loder, Wilmington, Del, assignor to E. I. du Pont de Nenours is mington, Del, a corporation ofCompany, Delaware Wi No Drawing. Application January 27, 1938, Serial No. 18,226 8. Claims. (C. 260-532) This invention relates to an improved, process for the preparation of propionic acid and its ethyl chloride, and the like, may likewise be used, esters and particularly to the preparation of pro although due to its availability, low cost, and pionic acid by the interaction of ethanol and car adaptability I prefer to employ ethanol as the bon monoxide in the presence of boron fluoride major raw material. as the catalyst. An aqueous solution of borontrifluoride is pre An object of the invention is to provide a ferred as the catalyst, which may be made in var 5 process for the preparation of propionic acid in , ious ways such, for example, as by the solution exceedingly high yields from ethanol and carbon of boron trifluoride in water; by the interaction O monoxide. A further object of the invention is of anhydrous hydrogen fluoride with boric oxide to provide a process for preparing propionic acid or boric anhydride; or, if desired, by the intro O and its ethyl ester from ethanol and carbon mon duction of boron trifluoride as a gas directly into oxide in the presence of such proportions of water the mixture of water, ethanol, ether and/or ester and boron trifluoride that substantially 100% prior to or during the reaction.
    [Show full text]
  • Product Overview Honeywell Team Provides Expertise in the Manufacture, Transport, Delivery, and Safe Handling of BF3
    For over 70 years, Honeywell has been the trusted Boron Trifluoride source for Boron Trifluoride (BF3) supply. The Product Overview Honeywell team provides expertise in the manufacture, transport, delivery, and safe handling of BF3. The #1 Choice for BF3 Gas and Complex Our high-performance BF3 commercial and technical services team is focused on your success. Our production experience, robust supply chain, large fleet, and product stewardship commitment gives us the ability to meet your expectations. Benefits of using Honeywell BF3 include: • Reliable supply and multiple inventory locations • Experienced and dedicated technical service support • Large modern fleet built and maintained to Honeywell standards with dedicated drivers • Superior supply chain with redundancies • Emergency response expertise • High quality products – ISO 9001 certified BF3 BF3 Methanol Complex BF3 Ether Complex UN ID Number UN 1008 UN 2922 UN 3286 Shipping Information Toxic, Corrosive Corrosive liquid, Toxic, NOS Flammable Liquid, Toxic, Corrosive, NOS Shipping Name Boron Trifluoride Boron Trifluoride Methanol Complex Boron Trifluoride Diethyl Etherate Form Compressed Gas Liquid Liquid Color Dense white cloud if exposed to moisture Colorless to yellowish Colorless to pale yellow Odor Strong pungent Strong pungent Strong pungent Chemical Formula BF3 CH4BF3O C4H10BF3O Boiling Point -148°F / -100°C Not determined 258.3°F / 125.7°C Melting Point -199.1°F / -128.4°C Not determined -76.7°F / -60.4°C Flash Point Not applicable 154°F / 67.8°C < 50°F / < 10°C Molecular Weight 67.81 g/mol 99.8 g/mol 141.94 g/mol Learn more To discuss your BF3 requirements, Although Honeywell International Inc.
    [Show full text]
  • SYNTHESIS and PROPERTIES of SOME ARALKYL Hymoperoxides
    SYNTHESIS AND PROPERTIES OF SOME ARALKYL HYmOPEROXIDES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By ARLO d / bCGGS, B.S., M.S. The Ohio State University 1954 Approved by: Department of Chemistry ACKNOWLEDGEMENT The author wishes to express sincere appreciation to Professor Cecil E. Boord for his advice and counsel during this investigation* Thanks also are due Dr. Kenneth W*. Greenlee for his continual interest and guidance and his cooperation in ex­ tending the facilities of the American Petroleum Institute Research Project 4-5* The financial support of this work by the Firestone Tire and Rubber Company is gratefully acknowledged* ii TABLE OF CONTENTS Page I. INTRODUCTION................................ 1 II. LITERATURE S URVEY ............... 2 III. STATEMENT OF THE PROBLEM.................... 10 IV. DISCUS5IŒ ........................... 11 A. Methods of Preparing Hydroperoxides .... 12 1. Preparation of hydroperoxides from alcohols ............. 12 a. a-methylbenzyl hydroperoxide ...... 12 b. benzyl hydroperoxide .......... l6 c. cinnamyl and a-phenylallyl hydroperoxides 17 d. 1,2,3,4-tetrahydro-l-naphthyl hydro­ peroxide ............ 22 e. a-indanyl hydroperoxide ........ 23 f. 0-, m- and p-methylbenzyl hydroperoxides 24 g. m- and p-methoxybenzyl hydroperoxides. 28 h. 1,1-diphenylmethyl hydroperoxide .... 31 i. 1,2-diphenylethyl hydroperoxide .... 32 j. 1-a-naphthyl- and l-J3-naphthylethyl hydroperoxides ........ 33 k. 1-styrylethyl hydroperoxide 35 1. 4-a-dimethylbenzyl and 4-methoxy-a- methylbenzyl hydroperoxides ...... 36 m. a-ethylbenzyl and a-ethyl-p-methylbenzyl hydroperoxides ....... ........ 36 n. a-n-propylbenzyl and a-isopropylbenzyl hydroperoxides .................... 37 0. a-2,5“trimethylbenzyl hydroperoxide .
    [Show full text]
  • One-Pot Syntheses of Irida-Polycyclic Aromatic Hydrocarbons† Cite This: Chem
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue One-pot syntheses of irida-polycyclic aromatic hydrocarbons† Cite this: Chem. Sci.,2019,10, 10894 a a a b a All publication charges for this article Yu Xuan Hu,‡ Jing Zhang,‡ Xiaoyan Wang, Zhengyu Lu, Fangfang Zhang, have been paid for by the Royal Society Xiaofei Yang,a Zhihua Ma,a Jun Yin, *a Haiping Xia b and Sheng Hua Liu *a of Chemistry Metalla-analogues of polycyclic aromatic hydrocarbons (PAHs) have captivated chemists with their fascinating structures and unique electronic properties. To date, metallabenzene, metallanaphthalene and metallaanthracene have been reported. Metalla-analogues with more complicated fused rings have rarely been reported. Herein, we have successfully synthesized a series of new iridafluoranthenes and fused-ring iridafluoranthenes ranging from pentacyclic to heptacyclic metallaaromatic hydrocarbons in Received 6th August 2019 high yields under mild reaction conditions for the first time. Their photophysical and redox properties Accepted 12th October 2019 were also explored using UV-vis spectroscopy and electrochemistry combined with TD-DFT DOI: 10.1039/c9sc03914g calculations. The present work may offer an important guideline for the design and construction of new rsc.li/chemical-science polycyclic metallaaromatic hydrocarbons and metalla-nanographenes. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction carbeneiridium compound by using an intramolecular C–H activation reaction.6b In 2018, they further developed irida- Polycyclic aromatic hydrocarbons (PAHs), as important compo- phenanthrene, iridanaphthalene and iridaanthracene from nents in the eld of organic chemistry, have attracted a signi- their corresponding methoxy(alkenyl)carbeneiridium inter- * cant amount of attention due to their wide range of applications mediates via reactions of [IrCp Cl(NCMe) (PMe3)]PF6 with 8 in organic light-emitting diodes,1 eld-effect transistors2 and diarylpropargyl alcohols.
    [Show full text]
  • Synthesis and Characterization of Boron Trifluoride Doped High Performance Polyaniline
    ISSN: 0973-4945; CODEN ECJHAO E-Journal of Chemistry http://www.ejchem.net 2012, 9(4), 2332-2337 Synthesis and Characterization of Boron Trifluoride Doped High Performance Polyaniline K. BASAVAIAH1*, D. SAMSONU2, AND A. V. PRASADA RAO1 1Department of Inorganic and Analytical Chemistry, Andhra University, Visakhapatnam- 530003, India 2Departments of Organic, Foods, Drugs and Water, Andhra University, Visakhapatnam- 530003, India [email protected] Received 28 July 2011; Accepted 4 October 2011 Abstract: We report simple synthesis of boron trifluoride (BF3) doped defect free high performance polyaniline (HPPANI) in two step method. Firstly, HPPANI was prepared via self-stabilization dispersion polymerization method in a heterogeneous reaction medium. Second step involves doping of emeraldine base form of HPPANI with boron trifluoride under reduced vacuum. The resultants BF3 doped HPPANI have been well characterized by using UV- Visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetry. The spectroscopic data indicated that the interaction between HPPANI and BF3.Thermogravimetry studies revealed that the BF3 doping improved the thermal stability of defects free PANI. Keywords: Conducting polymers; High performance PANI; Doping; Boron trifluoride; Thermal stability. Introduction Conducting polymers have attracted increasing attention because they offers the possibility of generation of novel materials with diverse applications for electromagnetic interference (EMI) shielding, rechargeable battery, chemical sensor, organic light emitting devices, corrosion devices, and microwave absorption1–5. Among conducting polymers, polyaniline (PANI) is the promising electrical conducting polymer due to its a broad range of tunable properties derived from its structural flexibility, good environmental stability, easy preparation in aqueous solution, and organic solvents, optical, electrical properties and unique redox chemistry6-7.
    [Show full text]
  • Detection of Phenethylamine, Amphetamine, and Tryptamine Imine By-Products from an Acetone Extraction
    Detection of Phenethylamine, Amphetamine, and Tryptamine Imine By-Products from an Acetone Extraction Mary A. Yohannan* and Arthur Berrier U.S. Department of Justice Drug Enforcement Administration Special Testing and Research Laboratory 22624 Dulles Summit Court Dulles, VA 20166 [email: mary.a.yohannan -at- usdoj.gov] ABSTRACT: The formation of imine by-products from phenethylamines, amphetamines, and tryptamines upon an acetone extraction is presented. These imine by-products were characterized using GC/MSD and exhibited preferential cleavage at the α-carbon of the alkyl chain. Further characterization of the imine by-products of phenethylamine and tryptamine was done using IR and NMR. KEYWORDS: phenethylamine, tryptamine, imine, acetone, schiff base, drug chemistry, forensic chemistry In most forensic laboratories, the solvents used to extract at the α-carbon on the alkyl chain. In addition to GC/MS, the drugs are chosen based upon their solubility properties and their imines formed from phenethylamine base and tryptamine base ability to not interact with the drug. In fact, there are very few were characterized by Fourier transform-infrared spectroscopy publications where a solvent used to extract a drug reacts with (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. the drug and forms by-products [1-3]. This laboratory recently discovered that an additional Experimental component was formed when acetone was used to extract a Solvents, Chemicals, and Materials sample containing a known tryptamine. Analysis by gas Acetone was ACS/HPLC grade from Burdick and Jackson chromatography/mass spectroscopy (GC/MS) of the acetone Laboratories (Muskegon, MI). Phenethylamine base and extract yielded an extra peak in the total ion chromatogram that tryptamine base were obtained from Sigma-Aldrich Chemicals was approximately half the abundance of the known tryptamine (Milwaukee, WI).
    [Show full text]
  • Gas Phase Ion/Molecule Reactions As Studied by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
    INIS-mf—10165 GAS PHASE ION/MOLECULE REACTIONS AS STUDIED BY FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY STEEN INGEMANN J0RGENSEN GAS PHASE ION/MOLECULE REACTIONS AS STUDIED BY FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY ACADEMISCH PROEFSCHRIFT ter verkrijging van de graad van doctor in de Wiskunde en Natuurwetenschappen aan de Universiteit van Amsterdam, op gezag van de Rector Magnificus dr. D.W. Bresters, hoogleraar in de Faculteit der Wiskunde en Natuurwetenschappen, in het openbaar te verdedigen in de Aula der Universiteit (tijdelijk in het Wiskundegebouw, Roetersstraat 15) op woensdag 12 juni 1985 te 16.00 uur. door STEEN INGEMANN J0RGENSEN geboren te Kopenhagen 1985 Offsetdrukkerij Kanters B.V., Alblasserdam PROMOTOR: Prof. Dr. N.M.M. Nibbering Part of the work described in this thesis has been accomplished under the auspices of the Netherlands Foundation for Chemical Research (SON) with the financial support from the Netherlands Organization for the Advancement of Pure Research (ZWO). STELLINGEN 1. De door White e.a. getrokken conclusie, dat het cycloheptatrieen anion omlegt tot het benzyl anion in de gasfase, is onvoldoende ondersteund door de experimentele gegevens. R.L. White, CL. Wilkins, J.J. Heitkamp, S.W. Staley, J. Am. Chem. Soc, _105, 4868 (1983). 2. De gegeven experimentele methode voor de lithiëring van endo- en exo- -5-norborneen-2,3-dicarboximide is niet in overeenstemming met de ge- postuleerde vorming van een algemeen dianion van deze verbindingen. P.J. Garratt, F. Hollowood, J. Org. Chem., 47, 68 (1982). 3. De door Barton e.a. gegeven verklaring voor de observaties, dat O-alkyl- -S-alkyl-dithiocarbonaten reageren met N^-dimethylhydrazine onder vor- ming van ^-alkyl-thiocarbamaten en ^-alkyl-thiocarbazaten, terwijl al- koxythiocarbonylimidazolen uitsluitend £-alkyl-thiocarbazaten geven, is hoogst twijfelachtig.
    [Show full text]
  • The Synthesis and Characterisation of a New Tröger's Base Content
    Sys Rev Pharm 2020;11(7):319-323 A multifaceted review journal in the field of pharmacy The Synthesis and Characterisation of a New Tröger’s Base Content Methoxy Group Sadiq A. Karim1, Mohammed H. Said2, Jinan A. Abd3, Asim A. Balakit4, Ayad F. Alkaim5 1,2,5Chemistry department, College of Science for women, University of Babylon, Iraq. 3Department of Laser physics, College of Science for women, University of Babylon, Iraq. 4Pharmaceutical Chemistry department, College of Pharmacy, University of Babylon, Iraq. Corresponding author: [email protected] ABSTRACT Five Tröger’s base (TB) molecules were synthesized by reaction aniline’s Keywords: Tröger base, heterocyclic compounds, chirality derivatives which content a methoxy group with a supplement of methylene (dimethoxymethane (DMM)) in present trifluoroacetic acid (TFA) as a solvent Correspondence: and catalyst. This method afforded a good ratio product between 62% to 99%, Sadiq A. Karim1 all products were conforming by FTIR, HRMs, 1HNMR, 13CNMR, and XRD. 1,2,5Chemistry department, College of Science for women, University of Babylon, Iraq. Corresponding author: [email protected] INTRODUCTION collected by filtration and was dried in a vacuum oven at The first Tröger’s base was create in 1887 by Julius Tröger 50 °C for 2 h. during his Ph.D. studied, this compound was called Tröger base 1 (TB1) which from the condensation of methanal 1- Synthesis of 2,9-Dimethoxy-6H,12H-5,11- with 4-aminotoluene in HCl-catalysed media.1 The TB1 methanodibenzo[b,f](1,5)diazocine (TB-OCH3-1) (2,8-dimethyl-6H,12H-5,11- General procedure was followed using m-anisidine (9.1 methanodibenzo[b,f][1,5]diazocine) was conformed ml, 10.00 g, 81.20 mmol), DMM (10.8 ml, 9.269 g, 121.80 structure through chemical reaction by M.
    [Show full text]
  • On the Road to Carbene and Carbyne Complexes
    ON THE ROAD TO CARBENE AND CARBYNE COMPLEXES Nobel Lecture, 11 December 1973 by ERNST OTTO FISCHER Inorganic Chemistry Laboratory, Technical University, Munich, Federal Republic of Germany Translation from the German text INTRODUCTION In the year 1960, I had the honour of giving a talk at this university* about sandwich complexes on which we were working at that time. I think I do not have to repeat the results of those investigations today. I would like to talk instead about a field of research in which we have been intensely interested in recent years: namely, the field of carbene complexes and, more recently, carbyne complexes. If we substitute one of the hydrogen atoms in a hydrocarbon of the alkane type - for example, ethane - by a metal atom, which can of course bind many more ligands, we arrive at an organometallic compound in which the organic radical is bound to the metal atom by a σ-bond (Fig. la). The earliest compounds of this kind were prepared more than a hundred years ago; the first was cacodyl, prepared by R. Bunsen (1), and then zinc dialkyls were prepared by E. Frankland (2). Later V. Grignard was able to synthesise alkyl magnesium halides by treating magnesium with alkyl halides (3). Grignard was awarded the Nobel Prize in 1912 for this effort. We may further recall the organo-aluminium compounds (4) of K. Ziegler which form the basis for the low pressure polymerisation, for example of ethylene. Ziegler and G. Natta were together honoured with the Nobel Prize in 1963 for their work on organometallic compounds.
    [Show full text]
  • Structural Characterization of Lignin Extracted With
    CELLULOSE CHEMISTRY AND TECHNOLOGY STRUCTURAL CHARACTERIZATION OF LIGNIN EXTRACTED WITH ALKALINE HYDROGEN PEROXIDE FROM FURFURAL RESIDUE CHANG-ZHOU CHEN,* MING-FEI LI,* YU-YING WU* and RUN-CANG SUN *,** *Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China ** State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China ✉Corresponding author: Run-Cang Sun, [email protected] Received August 6, 2013 Lignin from furfural residue was extracted with alkaline hydrogen peroxide at different temperatures and times. The structural features of lignins were characterized by elemental analysis, GPC, FT-IR, 1H NMR, 13 C NMR and Py-GC/MS. Results showed that the yield of lignin increased with the increase of reaction time and temperature. The maximum lignin yield of 41.4% (corresponding to the original lignin) was achieved by extraction at 80 ºC for 3 h. The average-molecular weight ( Mw) of the extracted lignins (780-850) was about 1/4 of that of the MWL (milled wood lignin) of furfural residue (2890), which indicated a severe degradation of furfural residue lignin under the treatment. Py-GC/MS analysis indicated that the major unit in lignins was p-hydroxycinnamyl (H), together with lower amounts of syringyl (S) and guaiacyl (G) units. The relative molar content of the H unit in the extracted lignins increased, as compared to MWL. Keywords : furfural residue, lignin, alkaline hydrogen peroxide, Py-GC/MS INTRODUCTION Furfural residue (FR) is a byproduct rich in are about 300 billion tons of lignin on the earth lignin and cellulose in the production of furfural.
    [Show full text]
  • The Selective Oligomerization of Ethylene Using Chromium Diphosphine Catalysts
    The Selective Oligomerization of Ethylene Using Chromium Diphosphine Catalysts and The Synthesis and Reactivity of Group 7 Carbonyl Derivatives Relevant to Synthesis Gas Conversion Thesis by Paul Richard Elowe In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, California 2009 (Defended July 17, 2008) 2009 Paul Richard Elowe All Rights Reserved ii Dédiée à ma famille, and to An iii Acknowledgments Spending the last five years of my life at Caltech has been quite an experience. When my undergraduate advisor Donald Berry told me that graduate studies at Caltech are unique, I could not realize how true that was at the time. There have been many good moments, and surely many challenging ones as well. I went from being John Bercaw’s academic grandson to his son in a matter of a few months in the summer of 2003. John has allowed me from the very beginning to work on the projects I was most interested in. His hands-off approach was instrumental in my rapid development as a chemist over the last few years. Thank you for everything you have brought me all these years. I also want to acknowledge Jay Labinger for his guidance. Always available, Jay answered many questions and helped out whenever I was stuck on a problem. I truly enjoyed playing tennis with you. I should also thank my thesis committee, Harry Gray, David Tirrell, and Jacqueline Barton, for great advice during candidacy, as well as throughout the proposals and thesis exams.
    [Show full text]