DOCSLIB.ORG

United States Patent (19) 11 Patent Number: 4,508,732 Hausberg Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) 11 Patent Number: 4,508,732 Hausberg Et Al United States Patent (19) 11 Patent Number: 4,508,732 Hausberg et al. (45) Date of Patent: Apr. 2, 1985 54 BASIC ETHERS USEFUL AS ANTIDEPRESSANTAGENTS OTHER PUBLICATIONS 75) Inventors: Hans-Heinrich Hausberg, Joullie et al., Chem. Abstr., 82,72789e (1975) (Abstract Weiterstadt; Helmut Pricher, of Ger. Offen. 2,413,605). Heppenheim; Jirgen Uhl, Seeheim; Klosa, Jour. fir Prartische Chemie, 311, 183 (1969). Christoph Seyfried, Primary Examiner-Nicky Chan Seehiem-Jugenheim; Klaus Minck, Attorney, Agent, or Firm-Millen & White Ober-Ramstadt, all of Fed. Rep. of Germany 57 ABSTRACT 73) Assignee: Merck Patent Gesellschaft mit Basic ethers of the formula beschrankter Haftung, Darmstadt, Fed. Rep. of Germany 21) Appl. No.: 459,928 22 Filed: Jan. 21, 1983 Related U.S. Application Data wherein Z is CH3-NR2-CH2CH2-CHR1-, (1-R2-3- 62 Division of Ser. No. 216,454, Dec. 15, 1980, Pat. No. piperidyl)-CHR3-, (1-R2-2-piperidyl)-CH2-CHR3- or 4,376,123. 1-R2-3-R- hexahydroazepinyl; R1 is cyclopropyl or Ar; R2 is H, alkyl of 1-4 C atoms, alkenyl of 2-4 C 30 Foreign Application Priority Data atoms, cycloalkylalkyl of 4-8 C atoms or benzyl; R3 is H Dec. 13, 1979 IDE Fed. Rep. of Germany ....... 295O135 or Ar; R4 is H or alkyl of 1-4 Catoms, Y is -O-CHQl 51 Int. Cl. ................... A61K 31/36; A61K 31/135; CHQ2-CH2-, -O-CHQ-CHQ2-CO-, -O- CO7C 93/14 CQl-CQ2-CO- or -CH2-CHQl-CHQ2-CO-; Q1 52 U.S. Cl. .................................... 514/466; 549/437; and Q2 are independently each H, alkyl of 1-4 Catoms, 564/352; 564/338; 564/337; 514/657 cycloalkyl or alkylcycloalkyl each of 3-6 total C atoms 58) Field of Search ....................... 564/352, 338, 337; or Ar; and Ar is phenyl or phenyl substituted by F, Cl, 424/330, 282; 549/437 alkoxy or alkylthio, each of 1-4 C atoms, methylenedi oxy or CF3; with the proviso that when Z is (CH3)2N 56) References Cited CH2CH2-CHR in 7-position and Y is -O- U.S. PATENT DOCUMENTS C(C6H5)=CH-CO- or -O-C(C6H5)=C(CH3)-CO-, R1 is cyclopropyl, or phenyl substituted by F, Cl, alk 3,476,767 11/1969 Bencze ................................ 564/352 3,506,653 4/1970 Fried ............. ... 564/352 oxy or alkylthio, each of 1-4C atoms, methylenedioxy 3,637,718 1/1972 Krämer et al. ... 546/196 or CF3; or a physiologically acceptable acid addition 4,194,009 3/1980 Molloy et al. ...................... 564/352 salt thereof, have valuable pharmacological properties, e.g., are antidepressants. FOREIGN PATENT DOCUMENTS 1357633 6/1974 United Kingdom . 7 Claims, No Drawings 4,508,732 1. 2 poxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy. BASIC ETHERS USEFUL AS ANTIDEPRESSANT Alkenyl (in the radical R2) is preferably allyl and is also AGENTS vinyl, propenyl, isopropenyl, 1-butene-1-yl, 1-butene 2-yl, 2-butene-1-yl, 2-butene-2-yl, 3-butene-1-yl, 3 This is a division of application Ser. No. 216,454 filed 5 butene-2-yl, 2-methyl-1-propene-1-yl, 2-methyl-1-pro Dec. 15, 1980, now U.S. Pat. No. 4,376,123. pene-2-yl or 2-methyl-2-propene-1-yl. Cycloalkylalkyl (in the radical R2) is preferably cyclopropylmethyl, but BACKGROUND OF THE INVENTION is also, for example, 1-cyclopropylethyl, 2-cyclo The present invention relates to new basic ethers propylethyl, 1-, 2- or 3-cyclopropylpropyl, 1-cyclopro having valuable pharmacological properties. O pyl-1-methylethyl, 1-, 2-, 3- or 4-cyclopropylbutyl, 1 Certain related compounds are known from the Jour cyclopropyl-1-methylpropyl, 1-, 2-, 3-, 4- or 5-cyclopro nal flir praktische Chemie, Volume 311, pages 183 to pylpentyl, cyclobutylmethyl, 1-cyclobutylethyl, 2 186 (1969), in particular 7-(1-phenyl-3-dimethylamino cyclobutylethyl, 1-, 2- or 3-cyclobutylpropyl, 1-, 2-, 3 propoxy)-flavone and 3-methyl-7-(1-phenyl-3-dime or 4-cyclobutylbutyl, cyclopentylmethyl, 1-cyclopen thylaminopropoxy)-flavone. However, it is stated in this 15 tylethyl, 2-cyclopentylethyl, 1-, 2- or 3-cyclopentylpro reference that the disclosed substances exhibit "no phar pyl, cyclohexylmethyl, 1-cyclohexylethyl, 2-cyclohex macodynamically usable properties'. In light of this ylethyl or cycloheptylmethyl. Alkylthio (in the radical statement, the valuable pharmacological properties of Ar) is preferably methylthio, but is also ethylthio, n the present new compounds are particularly surprising. propylthio, isopropylthio, n-butylthio, isobutylthio, SUMMARY OF THE INVENTION 20 sec-butylthio or tert-butylthio. It is an object of this invention to provide new com The radical Air is preferably phenyl and secondarily pounds which can be used for the preparation of medi p-fluorophenyl, p-chlorophenyl, p-methoxyphenyl, 3,4- cannents. methylenedioxyphenyl or m-trifluoromethylphenyl, Upon further study of the specification and appended 25 and also o-fluorophenyl, m-fluorophenyl, o-chlorophe claims, further objects and advantages of this invention nyl, m-chlorophenyl, o-methoxyphenyl, m-methox will become apparent to those skilled in the art. yphenyl, o-, m- or p-methylthiophenyl, 2,3- These objects have been attained by providing new methylenedioxyphenyl, o-trifluoromethylphenyl or p basic ethers of Formula I trifluoromethylphenyl. If several radicals Air are pres 30 ent in the same molecule, they can be identical or differ ent from one another. In detail, R is preferably phenyl, p-fluorophenyl, p-chlorophenyl or p-methoxyphenyl; R2 is preferably H or methyl and secondarily is preferably ethyl, allyl, 35 cyclopropylmethyl or benzyl; R3 is preferably H or wherein Z is CH3-NR2-CH2CH2-CHR1-, (1-R2 phenyl; and R4 is preferably H or methyl. 3-piperidyl)-CHR3-, (1-R2-2-piperidyl)-CH2-CH Accordingly, the radical Z is preferably 1-phenyl-3- R3- or 1-R2-3-R-4-hexahydroazepinyl; R1 is cyclo dimethylaminopropyl and secondarily is preferably propyl or Ar; R2 is H, alkyl of 1-4 C atoms, alkenyl of 1-phenyl-3-methylaminopropyl, 1-phenyl-3N-benzyl 2-4 C atoms, cycloalkylalkyl of 4-8 C atoms or benzyl; 40 N-methylaminopropyl, (3-piperidyl)-methyl, a-(3- R3 is H or Ar; R' is H or alkyl of 1-4 C atoms; Y is piperidyl)-benzyl, (1-methyl-3-piperidyl)-methyl, al-(1- -O-CHQl-CHQ2-CH2-, --O-CHQl-CH methyl-3-piperidyl)-benzyl, 2-(2-piperidyl)-ethyl, 1 Q2-CO-, -O-CQl=CQ2-CO- or -CH2-CH phenyl-2-(2-piperidyl)-ethyl, 2-(1-methyl-2-piperidyl)- Ql-CHQ2-CO-; Q and Q2 are independently each ethyl, 1-phenyl-2-(1-methyl-2-piperidyl)-ethyl, 4-hex H, alkyl of 1-4 C atoms, cycloalkyl of 3-6 C atoms or 45 ahydroazepinyl, 1-methyl-4-hexahydroazepinyl, 3 Ar; and Ar is phenyl or phenyl substituted by F, Cl, methyl-4-hexahydroazepinyl and 1,3-dimethyl-4-hex alkoxy or alkylthio, each of 1-4 C atoms, methylenedi ahydroazepinyl, and also, for example, 1-phenyl-3- oxy or CF3; with the proviso that when Z is methylethylaminopropyl, 1-phenyl-3-(N-methyl-N- (CH3)2N-CH2CH2-CHR in 7-position and Y is allylamino)-propyl, 1-phenyl-3-(N-methyl-N-cyclo -O-C(C6H5)=CH-CO- Or 50 propylmethylamino)-propyl, (1-ethyl-3-piperidyl)- -O-C(C6H5)=C(CH3)-CO-, R is cyclopropyl or methyl, a-(1-ethyl-3-piperidyl)-benzyl, (1-allyl-3- phenyl which is substituted by F, Cl, alkoxy or alkylthio piperidyl)-methyl, a-(1-allyl-3-piperidyl)-benzyl, (1- each of 1-4C atoms, methylenedioxy or CF3; and the cyclopropylmethyl-3-piperidyl)-methyl, a-(1-cyclo physiologically acceptable acid addition salts thereof. propylmethyl-3-piperidyl)-benzyl, (1-benzyl-3- 55 piperidyl)-methyl, a-(1-benzyl-3-piperidyl)-benzyl, 2 DETALED DISCUSSION (1-ethyl-2-piperidyl)-ethyl, 1-phenyl-2-(1-ethyl-2- The invention relates to the basic ethers of Formula I piperidyl)-ethyl, 2-(1-allyl-2-piperidyl)-ethyl, 1-phenyl and to their physiologically acceptable acid addition 2-(1-allyl-2-piperidyl)-ethyl, 2-(1-cyclopropylmethyl-2- salts. piperidyl)-ethyl, 1-phenyl-2-(1-cyclopropylmethyl-2- In R2, Rt., Ql and Q2, alkyl is preferably methyl, and 60 piperidyl)-ethyl, 2-(1-benzyl-2-piperidyl)-ethyl, 1-phe also ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbu nyl-2-(1-benzyl-2-piperidyl)-ethyl, 3-ethyl-4-hexahy tyl or tert-butyl. Cycloalkyl (in the radicals Q and Q2) droazepinyl, 1-methyl-3-ethyl-4-hexahydroazepinyl, is preferably cyclopropyl, cyclobutyl, cyclopenty or 1-ethyl-4-hexahydroazepinyl, 1-allyl-4-hexahydroazepi cyclohexyl and also 1-methylcyclopropyl, 2-methylcy nyl, 1-cyclopropylmethyl-4-hexahydroazepinyl or 1 clopropyl, 1-, 2- or 3-methylcyclobutyl, 1-, 2- or 3 65 benzyl-4-hexahydroazepinyl, 1-cyclopropyl-3- methylcyclopentyl, 1-ethylcyclopropyl or 2-ethylcy methylaminopropyl, 1-p-fluorophenyl-3-methylamino clopropyl and the like. Alkoxy (in the radical Ar) is propyl, 1-p-chlorophenyl-3-methylaminopropyl, -m- preferably methoxy and also ethoxy, n-propoxy, isopro trifluoromethylphenyl-3-methylaminopropyl, 1-cyclo 4,508,732 3. propyl-3-dimethylaminopropyl, 1-p-fluorophenyl-3- dimethylaminopropyl, 1-p-chlorophenyl-3-dime thylaminopropyl or 1-m-trifluoromethylphenyl-3-dime thylaminopropyl. The radicals Q and Q2 can be identical or different. Preferably one of these radicals is H or alkyl of 1-3 C atoms and the other is Hor Ar, Arbeing, in particular, or one of its salts, with an amine of Formula III phenyl, p-fluorophenyl, p-chlorophenyl, p-methox yphenyl, 3,4-methylenedioxyphenyl or n-trifluorome Z-X III thylphenyl. O wherein X is Cl, Br, I or OH and Z is as defined above, The radical Y is, accordingly, preferably -O-CH or with one of its reactive derivatives; and, if appropri Q3-CHQ-CH2- (wherein the radicals Q3 and Q ate, in a resulting compound of Formula I, converting a are each H or alkyl of 1-3 C atoms, but one of these secondary amino group by treatment with an alkylating, radicals preferably is H; chromans), -O-CHAr-CH 15 alkenylating, cycloalkylating or benzylating agent into Q-CH2- (flavans), -O-CHQ3-CHAr-CH2 the corresponding tertiary amino group, or converting (iso-flavans), -O-CHQ-CHQ-CO- (chroma an N-benzyl group by treatment with a reducing agent nones), -O-CHAr-CHQ-CO- (flavanones), into an NH group, and/or converting a resulting base of -O-CHQ-CHAr-CO- (iso-flavanones), Formula I by treatment with an acid into one of its -O-CQ-CQ-CO- (chromones), -O-- physiologically acceptable acid addition salts.
Load more

Recommended publications
  • (12) Patent Application Publication (10) Pub. No.: US 2005/0044778A1 Orr (43) Pub
    US 20050044778A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0044778A1 Orr (43) Pub. Date: Mar. 3, 2005 (54) FUEL COMPOSITIONS EMPLOYING Publication Classification CATALYST COMBUSTION STRUCTURE (51) Int. CI.' ........ C10L 1/28; C1OL 1/24; C1OL 1/18; (76) Inventor: William C. Orr, Denver, CO (US) C1OL 1/12; C1OL 1/26 Correspondence Address: (52) U.S. Cl. ................. 44/320; 44/435; 44/378; 44/388; HOGAN & HARTSON LLP 44/385; 44/444; 44/443 ONE TABOR CENTER, SUITE 1500 1200 SEVENTEENTH ST DENVER, CO 80202 (US) (57) ABSTRACT (21) Appl. No.: 10/722,127 Metallic vapor phase fuel compositions relating to a broad (22) Filed: Nov. 24, 2003 Spectrum of pollution reducing, improved combustion per Related U.S. Application Data formance, and enhanced Stability fuel compositions for use in jet, aviation, turbine, diesel, gasoline, and other combus (63) Continuation-in-part of application No. 08/986,891, tion applications include co-combustion agents preferably filed on Dec. 8, 1997, now Pat. No. 6,652,608. including trimethoxymethylsilane. Patent Application Publication Mar. 3, 2005 US 2005/0044778A1 FIGURE 1 CALCULATING BUNSEN BURNER LAMINAR FLAME VELOCITY (LFV) OR BURNING VELOCITY (BV) CONVENTIONAL FLAME LUMINOUS FLAME Method For Calculating Bunsen Burner Laminar Flame Velocity (LHV) or Burning Velocity Requires Inside Laminar Cone Angle (0) and The Gas Velocity (Vg). LFV = A, SIN 2 x VG US 2005/0044778A1 Mar. 3, 2005 FUEL COMPOSITIONS EMPLOYING CATALYST Chart of Elements (CAS version), and mixture, wherein said COMBUSTION STRUCTURE element or derivative compound, is combustible, and option 0001) The present invention is a CIP of my U.S.
    [Show full text]
  • Part I. Inversion of Secondary Cyclic Grignard Reagents
    This dissertation has been , 69-11,692 microfilmed exactly as received PECHHOLD, Engelbert, 1933- STUDIES OF THE BEHAVIOR AND GENERATION OF GARB ANIONS: PART I. INVERSION OF SECONDARY CYCLIC GRIGNARD REAGENTS. PART II. FRAGMENTATION OF AZOFORMATE SALTS AND ACYLAZO COMPOUNDS WITH BASES. The Ohio State University, Ph.D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan ©Copyright "by- Engelbert Pechhold 1969 STUDIES OF THE BEHAVIOR MD GENERATION OF CARBANIONS PART I. INVERSION OF SECONDARY CYCLIC GRIGNARD REAGENTS PART II. FRAGMENTATION OF AZOFORMATE SADIS AND ACYLAZO COMPOUNDS WITH BASES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Engelbert Pechhold * # # * * # The Ohio State University 1968 Approved by •pV-gpa.-t— Adviser Department of Chemistry DEDICATION To my wife, Ingrid, and my parents, whose love, understanding, and encouragement have made this venture possible. ii ACKNOWLEDaEMElWS I -wish to express my deepest appreciation to Professor Gideon Fraenkel for suggestinf^ this problem, and for his guidance and encouragement throughout the course of this research. His assistance in the preparation of this dissertation is gratefully acknowledged. It is an understatement to say that without his un­ usual courage of conviction and high standards for academic perfor­ mance, this work could not have come into being. I owe special debt of gratitude to my colleagues for many suimtü-ating discussions of chemical matters and otherwise. In particular, I wish to express my gratitute to Dr. Don Dix, Dr. Dave Mams, and James Morton, who gave me much insight in ny research.
    [Show full text]
  • Guide to the Jonas and Edna Kamlet / Kamlet Laboratories Records, 1913-1989
    Guide to the Jonas and Edna Kamlet / Kamlet Laboratories records, 1913-1989 Descriptive Summary Title : Jonas and Edna Kamlet / Kamlet Laboratories records Creator: Kamlet, Jonas Kamlet, Edna Dates : N/A ID Number : K27 Size: 190 boxes Abstract: This collection consists of records related to the Kamlet Laboratory and its founders. Chemist. Jonas kamlet and his wife, Edna, founded The Kamlet Laboratory (1940-1979) in New York City. The laboratory's work centered on the research and development of new methods for chemical products as well as identifying interested clients and selling rights to them. The laboratory also provided consultation services to a variety of businesses. Included are: personal papers, correspondence, professional correspondence, magazine clippings, newspaper clippings, photographs, drafts, publications, advertisements, announcements, price quotes, technical reports, test results, and scrapbooks. Includes personal papers, correspondence, professional correspondence, magazine clippings, newspaper clippings, photographs, drafts, publications, advertisements, announcements, price quotes, technical reports, test results, and scrapbooks. Language(s): English Repository: Special Collections University of South Florida Libraries 4202 East Fowler Ave., LIB122 Tampa, Florida 33620 Phone: 813-974-2731 - Fax: 813-396-9006 Contact Special Collections Administrative Summary Provenance: Kamlet, Jonas Kamlet, Edna Acquisition Information: Donation. Access Conditions: The contents of this collection may be subject to copyright. Visit the United States Copyright Office's website at http://www.copyright.gov/ for more information. Processing History: processed; Eight separate finding aids were initially made for these collections. However, these finding aids are now being combined to form one collection. Preferred Citation: Kamlet Laboratories Records, Special Collections Department, Tampa Library, University of South Florida, Tampa, Florida.
    [Show full text]
  • Lawrence Berkeley National Laboratory Recent Work
    Lawrence Berkeley National Laboratory Recent Work Title THE REACTION OF POTASSIUM GERMYL WITH ORGANIC HALIDES Permalink https://escholarship.org/uc/item/8bj224rn Author Dreyfuss, Robert Michael. Publication Date 1971 eScholarship.org Powered by the California Digital Library University of California • ! . - f - UCRL-20502 r : • r~ l1f I j >4 ~ ' l! . .z ·' :. I •'\ , ..\ 1:~ 1 ' -1. ; .. ~ (.., ~\)(: .,..J4··· .~ ·~·:.,., .. ,.:,..~·~-~01\ . • J I 'i ... THE REACTION OF POTASSIUM GERMYL WITH ORGANIC HALIDES Robert Michael Dreyfuss (Ph. D. Thesis) January 1971 AEC Contract No. W-7405-eng-48 TWO-WEEK LOAN COPY This is a Library Circulating Copy which may be borrowed for two weeks. ~or a personal retention copy, call Tech. Info. Dioision, Ext. 5545 1 c:: (} :::0 t-' I N 0 (J1 0 r., N ~ DISCLAIMER This document was prepared as an account of work sponsored by the United States Government. While this document is believed to contain correct information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or the Regents of the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or the Regents of the University of California.
    [Show full text]
  • Patent Office Paiented May 2, 1963
    United States Patent Office Paiented May 2, 1963 2 In addition, these prior metalation processes are gen 3,999,859 erally deemed unsuitable for commercialization due to TANSFETALATON PRESCESS Water E. Foster, Batca Rouge, La., assiggor to Eainy the difficulties and high costs connected with their use. Corporation, New York, N.Y., a corporation of Further, the prior processes require many separate proc Virginia eSS Steps as well as long periods for appreciable reaction No Draving. Fied Feb. 24, 1959, Ser. No. 794,817 which at best converts only half of the reactants, e.g., A2 Cains. (C. 262-665) toluene and sodium, to the desired product and com pletely degrades the chlorine values to sodium chloride. This invention relates to a method of preparing organic The above objectionable features of the prior art mate compounds and more particularly to the preparation of O rialiy increase the overall costs of the desired end prod aliphatic polyolefin hydrocarbons and organo alkali metal uct, and nake its manufacture by these processes com compounds. mercially unattractive. Aliphatic polyolefin hydrocarbons are extremely inter it is accordingly an object of the present invention to esting chemical compounds which are readily converted provide a process for the manufacture of aliphatic poly into valuable industrial materials by processes well known 5 olefin hydrocarbons. Another object is to provide a proc to those skilled in the art. Of particular interest are eSS of the above type which is suitable for manufacturing those long chain aliphatic polyolefin compounds where a very wide variety of aliphatic polyolefin hydrocarbons, in the unsaturation is located near the terminal carbons including many which were heretofore unknown or not of the molecular chain.
    [Show full text]
  • GEORG WITTIG Heidelberg, Federal Republic of Germany Translation from the German Text
    FROM DIYLS TO YLIDES TO MY IDYLL Nobel Lecture, 8 December 1979 by GEORG WITTIG Heidelberg, Federal Republic of Germany Translation from the German text Chemical research and mountaineering have much in common. If the goal or the summit is to be reached, both initiative and determination as well as perseverance are required. But after the hard work it is a great joy to be at the goal or the peak with its splendid panorama. However, especially in chemical research - as far as new territory is concerned - the results may sometimes be quite different: they may be disappointing or delightful. Looking back at my work in scientific research, I will confine this talk to the positive results (1). Some 50 years ago I was fascinated by an idea which I investigated experi- mentally. The question was how ring strain acts on a ring if an accumulation of phenyl groups at two neighboring carbon atoms weakens the C-C linkage and predisposes to the formation of a diradical (for brevity called diyl) (Fig. 1). Among the many experimental results (2) I choose the synthesis of the hydrocarbons 1 and 4 (3), which we thought capable of diyl formation. Starting materials were appropriate dicarboxylic esters, which we transformed into the corresponding glycols. While these were obtained under the influence of phenylmagnesium halide only in modest yield, phenyllithium proved to be superior and was readily accessible by the method of K. Ziegler, using bromobenzene and lithium. The glycolates resulting from the reaction with potassium phenylisopropylide formed - on heating with methyl iodide - the corresponding dimethyl ethers, which supplied the equivalent hydrocarbons 1 and 4 by alkali metal splitting and demetalation with tetramethylethylene dibromide.
    [Show full text]
  • Information to Users
    INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter free, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note wiU indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6” x 9” black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. UMI A Bell & Howell Infonnation Company 300 North Zed) Road, Ann Aibor MI 48106-1346 USA 313/761-4700 800/521-0600 NEW SYNTHETIC APPROACHES TO 3-NITROAZETIDINES PART I; NITRATION OF SALTS OF l-TERT-BUTYL-S-CYANOAZETIDINE PART 2: REACTION OF PRIMARY AMINES WITH 2-NITROALLYL ESTERS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Anthony F.
    [Show full text]
  • Organosodium and Organopotassium Compounds. Part II
    Organosodium and Organopotassium Compounds Part 11: Preparation and Synthetic Applications [I1 BY DR. M. SCHLOSSER UNION CARBIDE EUROPEAN RESEARCH ASSOCIATES, BRUSSELS (BELGIUM) AND ORGANISCH-CHEMISCHES INSTITUT DER UNIVERSITAT HEIDELBERG (GERMANY) 1 *I A selection of well established procedures for the preparation of’ the most common organo- sodium and organopotassium compounds is given. The wide synthetic applicability of organoalkali-metal compounds is shown by means of examples. Unlike Part I, Part II deals not only with “true” organoalkali compounds, but also with salt-like conzpounds such as sodium acetylides and sodiocarboxylic esters, since these possess considerable preparative value. A. Preparative Methods c) Halogen-metal exchange 1. From metal derivatives d) Cleavage of ethers a) Transmetalation e) Cleavage of carbon-carbon bonds b) Metalation with alkali amides f) Addition of metals to multiple bonds c) Other methods , B. Experimental procedures 2. Reactions with metals 1 1. Alkali metals a) Metal-metal exchangc I 2. Organoalkali-metal compounds b) Direct metalation i 3. Syntheses using organoalkali-metal compounds A. Preparative Methods Table I. Metalation of hydrocarbons ~ Metal- Hydrocarbon Yield ating Ref. Neu, conipound to be metalated [%I [bl A distinction is to be drawn between methods which lead to -agent [a the creation of new organometallic bonds by the action of Ethylene (31 Vinylsodium Icl elemental alkali metals, and those which merely effect trans- Propene Allylsodiuin 691dl fer of the organometallic bond from one organic residue to 131 I-Butene another. We shall first consider the latter type, in which a ’31 Crotylsodiuin 61[d] 2-Butene 1 readily accessible organometallic compound, or occasionally 131 2-Methylallylpotassiuni 63 an alkali metal amide or alkoxide, is used for the preparation Is0 butene i4i 78 of an organometallic reagent.
    [Show full text]
  • Kinetic and Other Studies of I^^Di
    KINETIC AND OTHER STUDIES OF I ^ ^ D I - AND TEI-ARYLMETHYL COMPOUNDS. by NIGEL JAMES WILLIAMS A Thesis presented for the degree of DOCTOR OF PHILOSOPHY in the Faculty of Science of the UNIVERSITY OF LONDON Bedford College, Lendon 1973* ProQuest Number: 10098265 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 complete 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 10098265 Published by ProQuest LLC(2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. Microform Edition © ProQuest LLC. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Acknowledgements. The author would like to thank Professor G.H. Williams for his interest and assistance through this research. The contributions of Dr. R. Bolton and of Dr. D. Murphy are also acknowledged, together with those of the author's colleagues. Bedford College is thanked for the provision of research facilities and of a Tutorial Research Studentship. To Biy parents< Abstract. The steric requirements of the three aromatic rings in the triphenylmethyl radical impose non-planarity upon the system, and a three-bladed propeller shape, where the blades are slightly feathered out of plane is thought to be a good approximation to the actual structure. Such a species, in appropiate circumstances could in principle exist in two geometric modifications* termed a symmetrical helix and an unsymmetrical helix.
    [Show full text]
  • Organic Seminar Abstracts
    HOBWwBfiwBflEt 1 '..., ;;;••.:•• |nraffl{ -;:!; ffiffl < In ffi X I B RARY OF THE U N IVERSITY Of ILLINOIS 8. 547 UGs 965-66 pt.l Return this book on or before the Latest Date stamped below. Theft, mutilation, and underlining of books are reasons for disciplinary action and may result in dismissal from the University. University of Illinois Library WftrH 1917 L161— O-1096 Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/organicsemi1965661univ ORGANIC SEMINAR ABSTRACTS I965-66 Semester I Department of Chemistry and Chemical Engineering University of Illinois SEMINAR TOPICS I Semester I965-I966 Preparation and Reactions of Perfluorothiocarbonyl Compounds Lennon H. McKendry 1 Organosilylalkali -Metal Compounds Marvin Coon. 10 Heterocyclic Aromatic Sulfur Compounds Adriane Gurak 17 Recent Advances in Polynucleotide Synthesis D. T. Browne 26 Olefin Induced Initiation of Free Radical Reactions Buren Ree 35 The Photochemical Lability of Aryl and Vinyl Esters . Robert J. Schacht : . 4U Optically Active Sulfoxides Ronald J. Trancik ......... 52 The Mechanism of Symmetrization of Organomercuric Halides Z. M. Holubec . 60 Cycloalkyne Intermediates Manley R. Johnston 69 Tetracyanoethylene Oxide and Related Epoxides Hayden Lipp 78 Hexaalkylbenzenes Mildred McDaniel 86 Reactions and Synthesis With Noble Metals Robert A. Gardiner 9k An Extended Hlickel Theory— Some Applications in the Field of Organic Chemistry Robert E. Cunningham, Jr 103 Study of Free Radicals by Flow Systems and ESR Dennis Chamot 112 Cyclodecapentaene s Kenneth Zahn 121 The Peroxide Oxgenation of Aromatic Compounds by Ionic Pathways Bill Foglesong 129 Structure Correlations by Gas Chromatography (The Kovats Retention Index System) Roy Swaringen 138 -2- Phosphoric Acid Ester Synthesis Carl L.
    [Show full text]
  • Working with Hazardous Chemicals
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • Steric and Electronic Influences in Organolithium Metalations John West Morton Jr
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1952 Steric and electronic influences in organolithium metalations John West Morton Jr. Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Morton, John West Jr., "Steric and electronic influences in organolithium metalations " (1952). Retrospective Theses and Dissertations. 13736. https://lib.dr.iastate.edu/rtd/13736 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. NOTE TO USERS This reproduction is the best copy available. UMI STEBIC AND ELECTRONIC INFLUENCES IN ORGANOLITHimi MliiTALATIONS by John West Morton, jr. A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Organic Chemistry Approved: Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Dean of'Graduate College Iowa State College 1952 UMI Number: DP12870 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted.
    [Show full text]