DOCSLIB.ORG

Download Date 28/09/2021 14:26:32

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Download Date 28/09/2021 14:26:32 Synthesis of compounds analogous to methyl sterculate Item Type text; Dissertation-Reproduction (electronic) Authors El Eris, Talib Mishin, 1930- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 28/09/2021 14:26:32 Link to Item http://hdl.handle.net/10150/565208 SYNTHESIS OF COMPOUNDS ANALOGOUS TO METHYL STERCULATE v • ' • \ ¥ ■ ' TaliU Me El Eris A Dissertation Submitted to the Faculty of the “COMMITTEE ON AGRICULTURAL BIOCHEMISTRY AND NUTRITION In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 1970 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Talib M» El Eris_________________________ entitled Synthesis of Compounds Analogous to Methyl Sterculate» be accepted as fulfilling the dissertation requirement of the degree o f ____________ Doctor of Philosophy______________ Dissertation Directorirector D a t e j After inspection of the final copy of the dissertation, the following members of the Final Examination Committee concur in its approval and recommend its acceptance:* XL-/ This approval and acceptance is contingent on the candidate’s adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the dissertation is evidence of satisfactory performance at the final examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the Uni­ versity Library to be made available to borrowers under rules of the Library,, Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made„ Requests for permission for extended quotation from or repro­ duction of this manuscript in whole dr in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the pro­ posed use of the material is in the interests of scholarshipe In all other instances, however, permis­ sion must be obtained from the author. ACKNOWLEDGMENTS The author wishes to express his. sincere appre­ ciation and gratitude; To Dr. H„ W„ Kircher for his helpful counsel and guidance in directing the course of this work and prepa­ ration of this dissertation. To Drs. A. R. Kemmerer and M. G. Vavich for en­ abling me to complete my graduate studies in the Depart­ ment of Agricultural Biochemistry and Nutrition. To Dr. Eo H. Pryde of the Oilseed Crops Labora­ tory of the Northern Research Laboratory, USDA, Peoria, Illinois, for supplying EAZ and MAZ. TABLE OF (CONTENTS Page LIST OF ILLUSTRATIONS..............___ ......... vi ABSTRACT .....................................o. v113. I. INTRODUCTION. .................................. 1 II. E ill J? ■ IMENTAL................................... 16 Preparation of Oleyl Alcohol............... 16 Preparation of Oleyl Tosylate.............. i? Preparation of 9-0ctadecene................ 18 Oxidation of 9-0ctadecene.................. 19 Preparation of Potassium Tert-hutoxide...=. 20 Preparation of 1,l-Dichloro-2,3-dioctyl- cyclopropane . @ . ./. ........................ 20 Preparation of 1,l-Dihromo-2,3"dioctyl- c y c1op ropane............................. 21 Preparation of 1,l-Dichloro-2-octyl-3- (7-carhomethoxyheptyl}-cyclopropane...... 25 Preparation of 9,10-Nonadecadiene ( D roc t y 1 .Al 1 en. e 2 7 Oxidation of Dioctyl Allene................ 29 Preparation of ^-Bromo-^-hutyrolactone..... 30 ' 2-0xo-3-tetrahydrofuranyl Triphenylphos- phonium Bromide pd-Triphenylphosphonium- (^-“hutyrolactone) Bromide. ............... 33 Cyclopropyltriphenylphosphonium Bromide.... 36 Attempted Synthesis of ^/-Triphenylphos- phonium-(^-undecalactone) Bromide ........ 36 Preparation of Phenyllithium............... 37 Heptylidenecyclopropane ..... 38 Bromination of Heptylidenecyclopropane..... 39 Hydrogenation of Heptylidenecyclopropane... 39 1,2-Me thylene-2-dode c ene................... 44 Ethyl-10,ll-methylene-9-undecenoate........ 46 Methyl-10,ll-methylene-9-undecenoate....... 48 III. DISCUSSION...................................... 55 iv V TABLE OF CONTENTS— Continued Page IV. ^5 e e e c.o o oe e e o oe e fre e ep o e e e e e e-e 9 .e0 o 6:6 e e e e e'o REFERENCES o@o*oe*@o@ee@eoe»e*#*oe*eo*ooe@o@oap LIST OF ILLUSTRATION'S Figure Page 1 . I.E. spectrum of 9-oetadecene in CS^ solution.. 22 2. GLC diagram comparing retention time of (a) 9-octadecene, (lo) dioctyl allene, and (c) 1 ,l-dichloro-2 ,3-dioctylcyclopropane, 175°, 18 It) He pressure....... 22 3. I.E. spectrum of 1,l-dichloro-2 ,3-dioctylcy­ clopropane in CS^ solution................. 23 4. I.R. spectrum of 1,l-dibromo-2 ,3-dioctylcy­ clopropane in CSg solution................. 23 5. I.R. spectrum of l,l-dichloro-2-octyl-3- (7-carbomethoxyheptyl)-cyclopropane in CS^ solution..................................... 26 6 . GLC diagram comparing retention time of (a) methyl oleate and (h) 1,l-dichloro-2- octyl-3-(7-carbomethoxyheptyl)-cyclo­ propane, 205P , 25 lb He pressure........... 26 7. I.R. spectrum of dioctyl allene in CS^ solution..................................... 31 8 . GLC diagram comparing retention time of (a) -bu tyro 1 act one and (b) tX-bromo-()-buty- rolactone, 175°, 18 lb He pressure......... 31 9. I.R. spectrum of ^-bromo-^-butyrolactone in CCl^ solution............................... 35 10. I.R. spectrum of 2-oxo-3-tetrahydrofuranyl triphenylphosphonium bromide in CHC1- solution.............................. 35 11. I.R. spectrum of cyclopropyltriphenylphos- phonium bromide in CHC1„ solution.......... 40 vi VII LIST OF ILLUSTRATIONS— Continued Figu re Page 12. GLC diagram comparing retention time of (a) hcptylidenecyclopropane and (t>) heptalde- hyde, 85°, 5 lb lie pressure................ 40 13. I.R. spectrum of heptylidenecyclopropane in CCl^ solution............................... 41 14. I.R. spectrum of brominated heptylidenecyclo­ propane in CCl^ solution................... 41 15. nmr spectrum of heptylidenecyclopropane....... 42 16. GLC diagram comparing retention time of (a) 1,2-methylene-2-dodecene and (b) decyl- aldehyde, 110° , 12 lb He pressure.......... 45 17. I.R. spectrum of 1,2-methylene-2-dodecene in CCl^ solution....................... 45 18. I.R. spectrum of brominated 1,2-methylene-2- dodecene in CCl^ solution.................. 47 19. GLC diagram comparing retention time of (a) ethyl-10, 11-methylene-9~undecenoate and (b) EAZ, 180°, 18 lb He pressure....... 47 20. I.R. spectrum of ethyl-10, 1l-methylene-9-un- decenoate in CCl^ solution................. 49 21. I.R. spectrum of hydrogenated ethyl-10,11- methylene-9-undecenoate in CCl^ solution... 49 22. I.R. spectrum of brominated ethyl-10, 11-methy­ lene-9-unde ceno ate in CCl^ solution....... 50 23. nmr spectrum of ethyl-10,ll-methylene-9- undecenoate.................................. 51 24. I.R. spectrum of methyl-10,ll-methylene-9- undecenoate in CCl^ solution............... 52 25. I.R. spectrum of hydrogenated methyl-10,11- methylene-9-undecenoate in CCl^ solution... 52 26 . nmr spectrum of methyl-10, 11-methylene-9- undecenoate.................................. 53 ABSTRACT gem-Dihalocyclopropane derivatives of 9-octa-* decene have been prepared by the Doering-Ho£fman and by the Seyferth methods and were reacted with alkyl- lithium reagents and sodium metal to produce dioctyl alienee The structure of dioctyl allene was verified by its infrared spectrum, gas chromatographic time as compared with that of 9-octadecene, and oxidation to pelargonic acid followed by GLC analysis of the meth­ ylated producte In one trial, the dioctyl allene could not be converted to the desired methyleneCyclo- propane, 9510-methylene-10-nonadecene, by reaction with zinc-copper couple and methylene iodide. A modified method for the £s£~bromination of ' y-butyrolactone is described. It does not require the use of large amount of catalyst (phosphorous tri­ bromide) and it gives higher yields than several of the methods found in the literature for bromination of carbonyl compounds in the alpha position. The methylenecyclopropanes, heptylidenecyclo- propane, 1,2-methylene-2-dodecene, methyl-10,11- methylene-9-undecenoate, and ethyl-10,11-methylene- 9-undecenoate have been synthesized by the Wittig vili ix reaction from cyelopropyltriphenylphosphonium bromide and the corresponding aldehydese Their structures have been verified by infrared and nmr spectra, by addition reactions such as hydrogenation, bromination, and hydrobromination, and by their gas chromatographic times as compared with those of the corresponding aldehydes0 The absorption frequencies at 3010, 1040, ttxa 963, and 935 cm". were present in the infrared spectra of the methylenecyclopropanes reported here* These bands are among the numerous typical bands reported in the literature for substituted methylenecyclopropane» The bands at 3010, 1000, 963? and 935 cm""*" did not appear in the infrared spectra of the hydrogenated, brpminated, and hydrobrominated derivatives of these methylenecyclopropaneso It is very interesting, in­ deed, to know that hydrogenation of these compounds resulted in a shift of
Load more

Recommended publications
  • (Vocs and Svocs) from Warm Mix Asphalt Incorporating Natural Zeolite and Reclaimed Asphalt Pavement for Sustainable Pavements
    sustainability Article Evaluation of Reductions in Fume Emissions (VOCs and SVOCs) from Warm Mix Asphalt Incorporating Natural Zeolite and Reclaimed Asphalt Pavement for Sustainable Pavements Javier Espinoza 1,2 , Cristian Medina 1,2, Alejandra Calabi-Floody 3 , Elsa Sánchez-Alonso 3 , Gonzalo Valdés 3 and Andrés Quiroz 1,2,* 1 Chemical Ecology Laboratory, Department of Chemical Sciences and Natural Resources, University of La Frontera, Temuco 4811230, Chile; [email protected] (J.E.); [email protected] (C.M.) 2 Biotechnological Research Center Applied to the Environment (CIBAMA), University of La Frontera, Temuco 4811230, Chile 3 Department of Civil Works Engineering, University of La Frontera, Temuco 4811230, Chile; [email protected] (A.C.-F.); [email protected] (E.S.-A.); [email protected] (G.V.) * Correspondence: [email protected] Received: 26 September 2020; Accepted: 10 November 2020; Published: 17 November 2020 Abstract: Conventional asphalt mixtures used for road paving require high manufacturing temperatures and therefore high energy expenditure, which has a negative environmental impact and creates risk in the workplace owing to high emissions of pollutants, greenhouse gases, and toxic fumes. Reducing energy consumption and emissions is a continuous challenge for the asphalt industry. Previous studies have focused on the reduction of emissions without characterizing their composition, and detailed characterization of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) in asphalt fumes is scarce. This communication describes the characterization and evaluation of VOCs and SVOCs from asphalt mixtures prepared at lower production temperatures using natural zeolite; in some cases, reclaimed asphalt pavement (RAP) was used.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 5,731,483 Stabel Et Al
    US005731483A United States Patent (19) 11 Patent Number: 5,731,483 Stabel et al. 45 Date of Patent: Mar. 24, 1998 54 RECYCLING OF PLASTICS IN A STEAM 52 U.S. Cl. .......................... 585/241; 585/648; 208/130 CRACKER 58 Field of Search ..................................... 585/241, 648; 208/130 75) Inventors: Uwe Stabel, Edingen-Neckarhausen; Helmut Woerz, Mannheim; Ruediger 56) References Cited Kotkamp, Limburgerhof; Andreas U.S. PATENT DOCUMENTS Fried, Bobenheim-Roxheim, all of Germany 5,364.995 11/1994 Kirkwood et al. ...................... 585,241 73) Assignee: BASFAktiengesellschaft, FOREIGN PATENT DOCUMENTS Ludwigshafen, Germany 2108.968 9/1983 Canada. 2094.456 10/1993 Canada. 21) Appl. No.: 553,658 502 618 9/1992 European Pat. Off. 567 292 10/1993 European Pat. Off. 22 PCT Filed: May 20, 1994 WO93/1812 9/1993 WIPO. (86 PCT No.: PCT/EP94/01647 Primary Examiner-Glenn Caldarola S371 Date: Nov. 17, 1995 Assistant Examiner-Bekir L. Yildirim Attorney, Agent, or Firm-Keil & Weinkauf S 102(e) Date: Nov. 17, 1995 57 ABSTRACT 87 PCT Pub. No.: WO95/03375 A process for recycling plastic waste in a steam cracker, PCT Pub. Date: Feb. 2, 1995 wherein a melt obtained from plastic waste is converted into 30 Foreign Application Priority Data products at from 400° 550° C., and a distillate fraction is separated off from the products at from 180° to 280° C. and Jul. 20, 1993 DEl Germany .......................... 43 24, 112.3 is fed as feed material to a steam cracker, Jan. 10, 1994 DEl Germany .......................... 4400 366.8 (51 int. Cl. .................. C07C 1/00; CO7C 4/22 9 Claims, 2 Drawing Sheets - N 5 AAA' U.S.
    [Show full text]
  • Catalytic Pyrolysis of Plastic Wastes for the Production of Liquid Fuels for Engines
    Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2019 Supporting information for: Catalytic pyrolysis of plastic wastes for the production of liquid fuels for engines Supattra Budsaereechaia, Andrew J. Huntb and Yuvarat Ngernyen*a aDepartment of Chemical Engineering, Faculty of Engineering, Khon Kaen University, Khon Kaen, 40002, Thailand. E-mail:[email protected] bMaterials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, 40002, Thailand Fig. S1 The process for pelletization of catalyst PS PS+bentonite PP ) t e PP+bentonite s f f o % ( LDPE e c n a t t LDPE+bentonite s i m s n HDPE a r T HDPE+bentonite Gasohol 91 Diesel 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) Fig. S2 FTIR spectra of oil from pyrolysis of plastic waste type. Table S1 Compounds in oils (%Area) from the pyrolysis of plastic wastes as detected by GCMS analysis PS PP LDPE HDPE Gasohol 91 Diesel Compound NC C Compound NC C Compound NC C Compound NC C 1- 0 0.15 Pentane 1.13 1.29 n-Hexane 0.71 0.73 n-Hexane 0.65 0.64 Butane, 2- Octane : 0.32 Tetradecene methyl- : 2.60 Toluene 7.93 7.56 Cyclohexane 2.28 2.51 1-Hexene 1.05 1.10 1-Hexene 1.15 1.16 Pentane : 1.95 Nonane : 0.83 Ethylbenzen 15.07 11.29 Heptane, 4- 1.81 1.68 Heptane 1.26 1.35 Heptane 1.22 1.23 Butane, 2,2- Decane : 1.34 e methyl- dimethyl- : 0.47 1-Tridecene 0 0.14 2,2-Dimethyl- 0.63 0 1-Heptene 1.37 1.46 1-Heptene 1.32 1.35 Pentane,
    [Show full text]
  • Title Crystallization of Stereospecific Olefin Copolymers (Special Issue on Physical Chemistry) Author(S) Sakaguchi, Fumio; Kita
    Crystallization of Stereospecific Olefin Copolymers (Special Title Issue on Physical Chemistry) Author(s) Sakaguchi, Fumio; Kitamaru, Ryozo; Tsuji, Waichiro Bulletin of the Institute for Chemical Research, Kyoto Citation University (1966), 44(4): 295-315 Issue Date 1966-10-31 URL http://hdl.handle.net/2433/76134 Right Type Departmental Bulletin Paper Textversion publisher Kyoto University Crystallization of Stereospecifie Olefin Copolymers Fumio SAKAGUCHI,Ryozo KITAMARU and Waichiro TSUJI* (Tsuji Laboratory) Received August 13, 1966 The stereoregularity of isotactic poly(4-methyl-1-pentene) was characterized and isomorphism phenomena were examined for the copolymeric systems of 4-methyl-1-pentene with several olefins in order to study the crystallization phenomena in these olefin copoly- mers polymerized with stereospecific catalysts. The structural heterogeneity or the fine crystalline structure of poly(4-methyl-1-pentene) could be correlated with its molecular structure by viewing this stereoregular homopolymer as if it were a copolymer. Cocrystallization or isomorphism phenomenon was recognized for the copolymeric systems of 4-methyl-1-pentene with butene-1, pentene-1, decene-1 and 3-methyl-1-butene, while no evidence of the phenomenon was obtained for the copolymeric systems with styrene and propylene. The degree of the isomorphism of those copolymers was discussed with the informations on the crystalline phases obtained from the X-ray study, on the constitution of the copolymeric chains in the amorphous phases obtained from the viscoelastic studies and on the other thermodynamical properties of these systems. INTRODUCTION Many works have been made with regard to the homopolymerization of olefins with stereospecific catalysts, i. e. complex catalysts composed of the combination of organometallic compound and transitional metallic compound.
    [Show full text]
  • Purification, Purity, and Freezing Points of Twenty-Nine Hydrocarbons of the API-Standard and API-NBS Series' by Anton J
    •c. FIGURE 27. Effect of testing conditions on structure of copper initially as annealed. Longitudinal sections etched in 3.5 parts glacial acetic acid and 4.5 parts nitric acid (cone), and 2 parts absolute alcohol, X750. rest Remarks Tempera- Strain ture rate ° F %/1,000 hr A 300 36. 4 Structure near axis of specimen 0.10 in. from position of complete fracture. B 300 8.3 Do. Journal of Research of the National Bureau of Standards Vol. 45, No. 2, August 1950 Research Paper 2122 Purification, Purity, and Freezing Points of Twenty-Nine Hydrocarbons of the API-Standard and API-NBS Series' By Anton J. Streiff,'~:i Laurel F. Soule,"- Charlotte M. Kennedy,'2 M. Elizabeth Janes,-;! Vincent A. Sedlak,2 Charles B. Willingham,4 and Frederick D. Rossini! This report describes the purification and determination of freezing points and purity of the following 29 hydrocarbons of tin- API-Standard and A.PI-NBS scries: 2,2,4,6,6- pentamethylheptane; i, I ,'2-i rimethylcyclopropane; cis-2-hexene; ci8-3-hexene; 2-methyl-l- pentene; 4-methyl-l-pentene; 3-methyl-trans-2-pentene; 4-methyl-cis-2-pentene; 4-methyl trans-2-pentene; 4,4-dimethyl-l-pentene; 4,4-dimei hyl-<rons-2-pentene: 2,3,3-trimei hy]-l- butene; tran8-4-octene; L-nonene; L-decene; L-undecene; L,3-butadiene;l,2-pentadiene; I ,ci8-3-pentadiene; I ,<rans-3-pentadienej l ,4-pentadiene; 2,3-pentadiene; 2-me1 hyl- L,3-buta- diene (isopreue); L,5-hcxadiene; 2,3-dimethyi-1,3-butadiene; l-<ii nenyl-1-cyclohexene- (4-vinyl- L-cyclohexene); cis-decahydronaphthalene; ^rons-decahydronaphi halene; 2,3-dihy- droindene (indan).
    [Show full text]
  • Catalytic Enantioselective Carbon-Carbon Bond Formation Using Cycloisomerization Reactions
    View Online / Journal Homepage / Table of Contents for this issue Chemical Science Dynamic Article LinksC< Cite this: Chem. Sci., 2012, 3, 2899 www.rsc.org/chemicalscience MINIREVIEW Catalytic enantioselective carbon-carbon bond formation using cycloisomerization reactions Iain D. G. Watsona and F. Dean Toste*b Received 30th April 2012, Accepted 7th June 2012 DOI: 10.1039/c2sc20542d This review describes important recent advancements in asymmetric cycloisomerization reactions. A wide variety of catalytic and asymmetric strategies have been applied to these reactions over the past twenty years. Cycloisomerization reactions have the ability to produce diverse polycyclic compounds in excellent yields and selectivity. They constitute a powerful and efficient strategy for asymmetric carbon- carbon bond formation in cyclic compounds. Enyne and related olefin cyclizations comprise the majority of reactions of this type and important advances have recently occurred in this area. However, significant changes have also occurred in the area of classical cyclization as well as intramolecular hydroacylation and C–H activation initiated cyclization and these will also be described. 1 Introduction The purpose of this review is to describe important new advances in asymmetric cycloisomerization reactions. In partic- The synthesis of rings is central to the art of organic synthesis. ular, this review will focus on enantioselective carbon-carbon Cyclic compounds abound in chemistry, from strained three bond forming cycloisomerizations. Many aspects of cyclo- membered rings to macrocyclic monsters. A common synthetic isomerization reactions have already been reviewed,3 including challenge is the creation of a ring within a certain target mechanistic4 and asymmetric aspects of the reaction.5 This compound.
    [Show full text]
  • Highly Efficient Olefin Isomerization Catalyzed by Metal Hydrides Derives from Dirhodium(Ii) Carboxylates and Catecholborane
    HIGHLY EFFICIENT OLEFIN ISOMERIZATION CATALYZED BY METAL HYDRIDES DERIVES FROM DIRHODIUM(II) CARBOXYLATES AND CATECHOLBORANE Gene A. Devora and Michael P. DoyleL' * Department of Chemistry, Trinity University, San Antonio, Texas 78212, USA Abstract. Dirhodium(ll) tetraacetate in combination with catecholborane catalyzes the iso- merization of alkenes and dienes. Effective isomerization occurs at 80-135°C with the use of only 0.1 mol % rhodium acetate. With 2-methyl-1,5-hexadiene the disubstituted double bond is prefer- entially isomerized. In addition, hydrogen transfer hydrogenation occurs with 1,4-cyclohexadienes. The mechanism of these reactions is proposed to involve organoborane addition across a Rh-0 bond which activates the catalyst for isomerization and hydrogenation. INTRODUCTION Catalytic isomerization of alkenes is a characteristic transformation of transition metal hy- drides that often accompanies hydrogenation1 and is one of the most thoroughly studied catalytic reactions.2"4 Compounds of cobalt, nickel, palladium, platinum, rhodium, and ruthenium are effective,2 but other transition metal compounds have also been employed for catalytic isomeriza- tions.2"4 Although the nature of this transformation is dependent on the catalyst, selectivity for alkene isomerization generally favors reactions with monosubstituted ethylenes over di- and tri-sub- stituted ethylenes. In the course of our investigations of the catalytic effectiveness of dirhodium(ll) tetrakis(carboxylates) we have uncovered a useful methodology for the generation of rhodium hydride species that, as we now report, are surprisingly effective for the isomerization of alkenes as well as for hydrogen transfer hydrogenation. MATERIALS AND METHODS Reactions were performed in a round bottom flask equipped with a screw cap that was fitted with a septum for convenient withdrawal of aliquots.
    [Show full text]
  • 7Alkenes and Alkynes I: Properties and Synthesis
    P1: PBU/OVY P2: PBU/OVY QC: PBU/OVY T1: PBU Printer: Bind Rite JWCL234-07 JWCL234-Solomons-v1 December 8, 2009 21:37 7 ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS. ELIMINATION REACTIONS OF ALKYL HALIDES SOLUTIONS TO PROBLEMS 7.1 (a) (E )-1-Bromo-1-chloro-1-pentene or (E )-1-Bromo-1-chloropent-1-ene (b) (E )-2-Bromo-1-chloro-1-iodo-1-butene or (E )-2-Bromo-1-chloro-1-iodobut-1-ene (c) (Z )-3,5-Dimethyl-2-hexene or (Z )-3,5-Dimethylhex-2-ene (d) (Z )-1-Chloro-1-iodo-2-methyl-1-butene or (Z )-1-Chloro-1-iodo-2-methylbut-1-ene (e) (Z,4S )-3,4-Dimethyl-2-hexene or (Z,4S )-3,4-Dimethylhex-2-ene (f) (Z,3S )-1-Bromo-2-chloro-3-methyl-1-hexene or (Z,3S )-1-Bromo-2-chloro-3-methylhex-1-ene 7.2 <<Order of increasing stability 7.3 (a), (b) H 2 Δ H° = − 119 kJ mol−1 Pt 2-Methyl-1-butene pressure (disubstituted) H 2 Δ H° = − 127 kJ mol−1 Pt 3-Methyl-1-butene pressure (monosubstituted) H2 − Δ H° = − 113 kJ mol 1 Pt 2-Methyl-2-butene pressure (trisubstituted) (c) Yes, because hydrogenation converts each alkene into the same product. 106 CONFIRMING PAGES P1: PBU/OVY P2: PBU/OVY QC: PBU/OVY T1: PBU Printer: Bind Rite JWCL234-07 JWCL234-Solomons-v1 December 8, 2009 21:37 ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS 107 H H (d) >> H H H (trisubstituted) (disubstituted) (monosubstituted) Notice that this predicted order of stability is confirmed by the heats of hydro- genation.
    [Show full text]
  • September 17, 2007
    Pre-Feasibility Report M/s. Neogen Chemicals Ltd. 1 1. Introduction M/s. Neogen Chemicals Ltd. is a new unit located at Plot No. Z/96/B SEZ Dahej, District: Bharuch, Gujarat. Now, the unit proposes to manufacture different type of synthetic organic dyes and pesticide products at above sited address. 2. Cost of Project Cost of existing project is 55 crore &, out of which 5 crore will be used for Environment Management System. 3. Production Capacity Production capacity is prescribe below: List of Products Sr. Name of Products Quantity No. (MT/Year) (MT/month) 1 Bromination and Chlorination of Alcohols 1.1. Ethyl Bromide 3500 291.67 1.2. n-Propyl Bromide 1.3. Iso Propyl Bromide 1.4. n-Butyl Bromide 1.5. Iso Butyl Bromide 1.6. Sec-Butyl Bromide 1.7. n-Hexyl Bromide 1.8. n-Heptyl Bromide 1.9. n-Octyl Bromide 1.10. n-Decyl Bromide 1.11. Lauryl Bromide 1.12. Cetyl Bromide 1.13. Myristyl Bromide 1.14. Stearyl Bromide 1.15. 1,2 Dibromo Ethane 1.16. 1,3 Dibromo Propane 1.17. 1,4 Dibromo Butane 1.18. 1,5 Dibromo pentane M/s. Neogen Chemicals Ltd. 2 Sr. Name of Products Quantity No. (MT/Year) (MT/month) 1.19. 1,6 Dibromo Hexane 1.20. 1 Chloro 2 Ethyl Hexane 1.21. 6 Chloro 1 Hexanol 1.22. 3 Chloro Propanol 1.23. 1,6 Dichloro Hexane 1.24. Cyclo Propyl Methyl Bromide 1.25. Cyclo Pentyl Bromide 1.26. Cyclo Pentyl Chloride 2. Bromination of Organic Acids and Esterification thereof 2.1.
    [Show full text]
  • ' United "States Patent Office
    Patented on. 20, 1.942 I . 2,299,411 ' UNITED "STATES PATENT OFFICE CATALYZED HYDROBROMINATION OF UN SATURATED ORGANIC COMPOUNDS Fredericlr Rust and William E. Vaughan, ' Berkeley, Calif., assignors. to Shell Develop ment Company, San Francisco, Calif., a corpo ration of Delaware No Drawing. 4 Application August 25, 1941, Serial No. 408,212 - 9'Claims. (01. 260-663) ' This invention relates to an improved process for the hydrobromination of unsaturated organic hydes and metal alkyls which tend to initiate I compounds, and more particularly to improve the reaction chains. v ments in the method of controlling the addition It is known that the presence of peroxide: orv of hydrogen bromide to unsymmetrical organic of peroxide-forming compounds in unsaturated compounds containing at least one ole?nic or organic compounds, e. g. unsaturated hydrocar acetylenic linkage to produce addition products bons, is undesirable. For example, organic per of a predetermined character. oxides, when present even in relatively small con It is known that hydrogen halides may be centrations, tend to catalyze the polymerization of a large number of unsaturated hydrocarbons, . added to unsaturated hydrocarbons and to var 10 ious unsaturated derivatives thereof. In fact, and particularly diole?ns. As to the “abnormal” in 1870 Markowniko? stated that “if an addition ofhydrogen bromide to unsaturates by metrical hydrocarbon combines with a halogen effecting the reaction under the deliberate in acid, the halogen adds to the carbon atom with ?uence, of light, and particularly of ultra-violet fewer hydrogen atoms, i. e. to the carbon atom radiations having wave-lengths of below about which is more'under the in?uence of other car' 2900 to 3000 Angstrom units, such processes ne bon atoms.” The same investigator further de cessitate the use of special equipment, such as termined that when a hydrogen halide is added reaction vessels provided with or containing to a halogenated unsaturated compound such as lamps made of quartz Or other suitable mate rials, e.
    [Show full text]
  • Chemical Compatibility Chart X
    Chemical Compatibility Chart Below is a chart adapted from the CRC Laboratory Handbook, which groups various chemicals in to 23 groups with examples and incompatible chemical groups. This chart is by no means complete but it will aid in making decisions about storage. For more complete information please refer to the MSDS for the specific chemical. Examples of each group can be found on the next pages. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Monomers Polymerizable Esters Alcohols, Glycols, Glycol Ether Amines and Alkanolamines Halogenated Compounds Aldehydes Acetaldehyde Saturated Hydrocar Aromatic Hydrocarbons Acid Anhydrides Alkylene Oxides Inorganic Acids Petrolium Oils Organic Acids Cyanohydrins Phosphorus Ammonia Group Halogens Ketones Caustics Phenols Nitriles Olefins Ethers Number/Chemical Esters Type bons Inorganic 1 x x x x x x x x x x x x x x x x x Acids 2 Organic Acids x x x x x x x x x x 3 Caustics x x x x x x x x x x x x x Amines and 4 x x x x x x x x x x x x Alkanolamines Halogenated 5 x x x x x x Compounds Alcohols, 6 Glycols, Glycol x x x x x x Ether Aldehydes 7 x x x x x x x x x x x x Acetaldehyde 8 Ketones x x x x x x Saturated 9 x Hydrocarbons Aromatic 10 x x Hydrocarbons 11 Olefins x x x 12 Petrolium Oils x 13 Esters x x x x x Monomers 14 Polymerizable x x x x x x x x x x x x Esters 15 Phenols x x x x x x x Alkylene 16 x x x x x x x x x x x x Oxides 17 Cyanohydrins x x x x x x x x x 18 Nitriles x x x x x x 19 Ammonia x x x x x x x x x x x 20 Halogens x x x x x x x x x x x x x x 21 Ethers x x x 22 Phosphorus x x x x Acid 23 x x x x x x x x x x Anhydrides X - Indicates chemicals that are incompatible and should not be stored together.
    [Show full text]
  • Properties and Synthesis. Elimination Reactions of Alkyl Halides
    P1: PBU/OVY P2: PBU/OVY QC: PBU/OVY T1: PBU Printer: Bind Rite JWCL234-07 JWCL234-Solomons-v1 December 8, 2009 21:37 7 ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS. ELIMINATION REACTIONS OF ALKYL HALIDES SOLUTIONS TO PROBLEMS 7.1 (a) ( E )-1-Bromo-1-chloro-1-pentene or ( E )-1-Bromo-1-chloropent-1-ene (b) ( E )-2-Bromo-1-chloro-1-iodo-1-butene or ( E )-2-Bromo-1-chloro-1-iodobut-1-ene (c) ( Z )-3,5-Dimethyl-2-hexene or ( Z )-3,5-Dimethylhex-2-ene (d) ( Z )-1-Chloro-1-iodo-2-methyl-1-butene or ( Z )-1-Chloro-1-iodo-2-methylbut-1-ene (e) ( Z,4 S )-3,4-Dimethyl-2-hexene or ( Z,4 S )-3,4-Dimethylhex-2-ene (f) ( Z,3 S )-1-Bromo-2-chloro-3-methyl-1-hexene or (Z,3 S )-1-Bromo-2-chloro-3-methylhex-1-ene 7.2 < < Order of increasing stability 7.3 (a), (b) H − 2 ∆ H° = − 119 kJ mol 1 Pt 2-Methyl-1-butene pressure (disubstituted) H2 − ∆ H° = − 127 kJ mol 1 Pt 3-Methyl-1-butene pressure (monosubstituted) H2 − ∆ H° = − 113 kJ mol 1 Pt 2-Methyl-2-butene pressure (trisubstituted) (c) Yes, because hydrogenation converts each alkene into the same product. 106 CONFIRMING PAGES P1: PBU/OVY P2: PBU/OVY QC: PBU/OVY T1: PBU Printer: Bind Rite JWCL234-07 JWCL234-Solomons-v1 December 8, 2009 21:37 ALKENES AND ALKYNES I: PROPERTIES AND SYNTHESIS 107 H H (d) > > H H H (trisubstituted) (disubstituted) (monosubstituted) Notice that this predicted order of stability is confirmed by the heats of hydro- genation.
    [Show full text]