DOCSLIB.ORG

Glyoxylic Acid. by VICTORJOHN HARDING and CHARLESWEIZMANN

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Glyoxylic Acid. by VICTORJOHN HARDING and CHARLESWEIZMANN View Article Online / Journal Homepage / Table of Contents for this issue 1126 HARDlNC3 AND WEIZMANN : SYNTHESIS OF XCIV.-Synthesis of 6-Carboxy-3: 4-dimethoxyphenyl- glyoxylic Acid. By VICTORJOHN HARDING and CHARLESWEIZMANN. AMONGthe products of the oxidation of trimethylbrazilin by means of warm potassium permanganate, there was found to occur a dibasic acid possessing the empirical formula C,,H,,O,. This acid, which was isolated and investigated in these laboratories by W. H. Perkin, jun., was shown to be 6-carboxy-3: 4-dimethoxy- phenylglyoxylic acid (I) [“ dimethoxycarboxybenzoylformic acid ”1 (Trans., 1902, 81, 1022). In the present communication the authors describe the synthesis of this acid from 4 : 5-dimethoxy-o-methyZacetophenone(11) : MeO/\C02H MeOAMe MeO/\Me MeOl ‘CO*C02H MeOI ICOMe Me01 /CO*CO,H \/ \/ \/ (1.1 (11.) (111.) This ketone is easily prepared by the condensation of acetyl chloride and homocatechol dimethyl ether by means of aluminium chloride. When oxidised by warm potassium permanganate there is first isolated 4 : 5-clinz,ethoxy-o-tolylgl~o~l~cacid (111). Further oxidation converts the methyl group into a carboxy-group, and leads to the production of 6-carboxy-3 : 4-dimethoxyphenylglyoxylic acid. Although it has not been found possible directly to compare the synthetical acid with that obtained from trimethylbrazilin, the Published on 01 January 1910. Downloaded by New York University 27/02/2016 21:27:57. authors do not think there can be much doubt as to their identity. The following are the properties of the synthetical acid: 1. Calcium cE’loride, with a neutral solution of the ammonium salt, gives no precipitate in the cold, but on warming, the crystalline calcium salt separates af; once. 2. The acid, separated by means of the calcium salt, crystallises with two molecules of water in small, brown, soluble prisms. 3. The silver salt is derived from the anhydrous acid. 4. The melting point of a specimen of acid dried in the water- oven was found to be 148O (Perkin gives 150O). With the exception of the slight difference in the melting point, these properties agree exactly with those described by Perkin (Zoc. cit.). As, however, a difference was found between the oxime of the synthetical acid and that obtained by Perkin, it was judged necessary to convert the synthetical product into some derivative which would determine absolutely the position of the oxalyl group, View Article Online 6-CARBOXY-3 : 4-DIMETHOXYPHENYI~GLYOXYLZCACID. 1J 27 because it is easily conceivable that an acid possessing the con- stitution : CO*CO,€I might show properties almost identical with the isomeric acid, as, indeed, is shown in the case of the two similarly isomeric hemipinic acids. In order to determine this point, the 6-carboxy-3: 4-cli- methoxyphenylglyoxylic acid was converted into m-hemipinic acid. This was accomplished by the distillation of the silver salt, by which method a quantitative yield of m-hemipinic anhydride was obtained. This proves beyond all doubt the constitution of the synthetical acid, and establishes its identity with the acid obtained by the oxidation of trimethylbrazilin. 4 : 5-Dimethoxy-o-methylacetophenone,when warmed in glacial acetic acid solution with a few drops of concentrated nitric acid, undergoes a remarkable reaction; the acetyl group is displaced by a nitro-group, with the production of nitrohomocatechol dimethyl ether : &f.P oqm3 nl.Oj/N 0, ' The displacement of a carboxy-group by a nitro-group is well known, and Salway (Trans., 1909, 95, 1155) has shown that the aldehyde group can also be displaced by a nitro-group. The displace- ment of an acetyl group by a nitro-group, however, does not seem to have been previously observed, and it is hoped shortly to com- municate the results of investigations in this direction. It is Published on 01 January 1910. Downloaded by New York University 27/02/2016 21:27:57. worthy of note that the displacement of the acetyl group can be effected by warm dilute aqueous nitric acid, the temperature of the reaction and concentration of the acid apparently having very little influence on the displaccment. E x P E R I M E N T A L. 4 : 5-I) ini e thoz y-o-m e t hy lu c e t ophen,on e, C,H,Me (0Me) CO Me. This ketone is easily obtained by condensing acetyl chloride (30 grams) with homocatechol dimethyl ether (50 grams), dissolved in 200 C.C. of carbon disulpliide, by means of aluminium chloride (100 grams). The reaction is maintained at the ordinary tem- perature for twenty-four hours, when it is heated for a further two hours on the water-bath. The dark red product is decom- posed by water, and the carbon disulphide removed by distillation in a current of steam. The dark brown residual oil is then View Article Online 1128 HARDING AND WEIZMANN : SYNTHESIS OF extracted by means of ether, washed with a dilute solution of potassium hydroxide, dried, and distilled. The ketone, which distils at 204O/70 mm., rapidly solidifies in the receiver, and is purified by crystallisation from methyl alcohol or light petroleum of high boiling point : 0.1409 gave 0.3503 CO, and 0.0941 H,O. C=67.7; H=7.4. CllH140, requires C = 68.0 ; H = 7.3 per cent. 4 : 5-Dimethoxy-o-metl~ylacetop7~enonecrystallises in short, colour- less needles, melting at 68O. It possesses an aromatic odour, recall- ing that of homocatechol dimethyl ether. The phenylhydrazone, prepared in the usual way, crystallises from acetic acid. It shrinks together at 168O, and decomposes at 170° : 0.2020 gave 18.5 C.C. N, (moist) at 17O and 725 nim. N=10*1. C17H,,0,N2 requires N = 9.9 per cent. The semicarbazone decomposes at 186O. Pipe~onylidene-4: 5-~im.et7~oxy-o-met7aylaceto~~~~enone, C,H,MeCOMe,) *CO*CH:CH*C,H,:O,: CH,. This derivative is prepared by dissolving molecular quantities of 4 : 5-dimethoxy-o-methylacet~phenoneand piperonal in methyl alcohol, adding a few drops of 50 per cent. aqueous potassium hydroxide, and boiling for a short time. On dilution with water, the resulting oil solidifies after some time. This is collected and crystallised from alcohol, from which it separates in golden-yellow needles, melting at 108-109° : 0.1152 gave 0’2916 CO, and 0.0602 H,O. C = 69.1 ; H =5.8. C,9H,80, requires C = 69.6 ; H = 5.5 per cent.. Published on 01 January 1910. Downloaded by New York University 27/02/2016 21:27:57. Oxidation of 4 : 5-Dimethoxy-o-rr~~ethylacetophenoneby means of Alkaline Potassium Permangunate. A.-Fornaation of 4 : 5-Dinsqethoxy-o-tolylglgoxylic Acid, C,H,Me(OMe)z*CO C0,H. Ten grams of 4 : 5-dimetlioxy-o-methylacetophenoneare added to 8 grams of sodium carbonate dissolved in 100 C.C. of water, and heated on the water-bath. Sixty grams of potassium permanganate, dissolved in 600 C.C. of water, are then added. The oxidation proceeds slowly. When the pink colour of the permanganate has disappeared, the manganese dioxide is collected, washed several times with boiling water, and the combined filtrates are evaporated to a small bulk on the water-bath. On acidifying with hydro- chloric acid, 4 : 5 -dimethoxy-o-tolylglyoxylic acid gradually crys- tallises out. After recrystallisation from hot water, it melts at 155O. View Article Online 6-CARBOXY-Q : 4-DINETHOXYPHENYLGLYOXYLIC ACID. 1129 0.1130 gave 0.2434 CO, and 0.0520 H20. C=58*8; H=5.1. C,,H,,O, requires C = 58.9 ; H = 5.3 per cent. 4 : 5-Dimethox~-o-toZylgZ~ox~licacid crystallises from water in short needles, and is insoluble in cold benzene. Its solution in concentrated sulphuric acid develops a cherry-red colour. B.-Synthesis of 6-Curb oxy-3 : 4-d.i~net7~oxyphenyZglyoxyZ~cAcid, C0,H*C,H2(0Me),*CO*C0,H. This acid is obtained by the oxidation of 4 : 5-dimethoxy-o-methyl- acetophenone under the following conditions. The ketone (20 grams) is added to sodium carbonate (15 grams) dissolved in water (100 c.c.), and a 10 per cent. solution of potassium permanganate (150 grams) added gradually, the operation being conducted on the water-bath. When the oxidation is complete, the manganese dioxide is collected, extracted several times with boiIing water, and the combined filtrates and washings are evaporated to a very small bulk, acidified with hydrochloric acid, mixed with sand, and then evaporated to complete dryness. The dry mass is then extracted by means of ether in a Soxhlet apparatus, and on evaporating the ethereal extract a viscid liquid is obtained, which crystallises after some time. The silver salt was prepared for analysis, and, as observed by Perkin (Trans., 1902, 81, 1023), is derived from the anhydrous acid. (Found, C = 28.2 ; H = 1.7 ; Ag = 45.8. Calc., C=28*2; H=1.7; Ag=46.1 per cent.) In order to prepare an acid corresponding exactly in properties with that described by Perkin (Zoc. cit.), a portion of the crude oily acid, obtained direct from the oxidation, was dissolved in water, neutralised with ammonia, and boiled with a solution of calcium chloride. The Published on 01 January 1910. Downloaded by New York University 27/02/2016 21:27:57. calcium salt, which separated during the heating, was collected and decomposed by hydrochloric acid, when, after some time, the 6-carbbxy-3 : 4-dimethoxyplienylglyoxylic acid crystallised in small, brown prisms. These were collected and dried on porous porcelain in the air for twenty-four hours. (Found, C = 45.0 ; H = 4.5.
Load more

Recommended publications
  • Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances 2017
    INTERNATIONAL NARCOTICS CONTROL BOARD Precursors and chemicals frequently used in the illicit manufacture of narcotic drugs and psychotropic substances 2017 EMBARGO Observe release date: Not to be published or broadcast before Thursday, 1 March 2018, at 1100 hours (CET) UNITED NATIONS CAUTION Reports published by the International Narcotics Control Board in 2017 The Report of the International Narcotics Control Board for 2017 (E/INCB/2017/1) is supplemented by the following reports: Narcotic Drugs: Estimated World Requirements for 2018—Statistics for 2016 (E/INCB/2017/2) Psychotropic Substances: Statistics for 2016—Assessments of Annual Medical and Scientific Requirements for Substances in Schedules II, III and IV of the Convention on Psychotropic Substances of 1971 (E/INCB/2017/3) Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances: Report of the International Narcotics Control Board for 2017 on the Implementation of Article 12 of the United Nations Convention against Illicit Traffic in Narcotic Drugs and Psychotropic Substances of 1988 (E/INCB/2017/4) The updated lists of substances under international control, comprising narcotic drugs, psychotropic substances and substances frequently used in the illicit manufacture of narcotic drugs and psychotropic substances, are contained in the latest editions of the annexes to the statistical forms (“Yellow List”, “Green List” and “Red List”), which are also issued by the Board. Contacting the International Narcotics Control Board The secretariat of the Board may be reached at the following address: Vienna International Centre Room E-1339 P.O. Box 500 1400 Vienna Austria In addition, the following may be used to contact the secretariat: Telephone: (+43-1) 26060 Fax: (+43-1) 26060-5867 or 26060-5868 Email: [email protected] The text of the present report is also available on the website of the Board (www.incb.org).
    [Show full text]
  • Safrole and the Versatility of a Natural Biophore Lima, L
    Artigo Safrole and the Versatility of a Natural Biophore Lima, L. M.* Rev. Virtual Quim., 2015, 7 (2), 495-538. Data de publicação na Web: 31 de dezembro de 2014 http://www.uff.br/rvq Safrol e a Versatilidade de um Biofóro Natural Resumo: Safrol (1) obtido de óleos essenciais de diferentes espécies vegetais tem ampla aplicação na indústria química como precursor sintético do butóxido de piperonila, piperonal e de fármacos como a tadalafila, cinoxacina e levodopa. Do ponto vista toxicológico, é considerado uma hepatotoxina por mecanismo de bioativação metabólica conduzindo a formação de intermediários eletrofílicos, e tem sido descrito como inibidor de diferentes isoenzimas da família CYP450. A versatilidade de sua estrutura, permitindo várias transformações químicas, e a natureza biofórica de sua unidade benzodioxola ou metilenodioxifenila conferem-lhe características singulares, que o tornam atrativo material de partida para a síntese de compostos com distintas atividades farmacológicas. Exemplos selecionados de compostos bioativos, naturais e sintéticos, contendo o sistema benzodioxola serão comentados, incluindo aqueles provenientes de contribuição específica do LASSBio®. Palavras-chave: Safrol; benzodioxola; metilenodioxi; CYP450; bióforo; compostos bioativos. Abstract Safrole (1), obtained from essential oils from different plant species, has wide application in the chemical industry as a synthetic precursor of piperonyl butoxide, piperonal and drugs such as tadalafil, cinoxacin and levodopa. From the toxicological point of view, it is considered a hepatotoxin through metabolic bioactivation, leading to the formation of electrophilic metabolites, and has been described as an inhibitor of different CYP450 isoenzymes. The versatility of its structure, allowing various chemical transformations, and the biophoric nature of its benzodioxole or methylenedioxy subunit, give it unique features and make it an attractive starting material for the synthesis of compounds with different pharmacological activities.
    [Show full text]
  • THE THIOBARBITURIC ACID TEST in IRRADIATION-STERILIZED BEEF By
    THE THIOBARBITURIC ACID TEST IN IRRADIATION-STERILIZED BEEF by NORMAN LEE SMITH A THESIS submitted to OREGON STATE COLLEGE in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE June 1959 APPROVED: Redacted for Privacy Associate Professor of Chemistry In Ghare of Major Redacted for Privacy Chairman of Department of Chemistry Redacted for Prîvacy Chairman of choo1 Graduate Committee Dean of Graduate School Date thesi9 19 presented July 10, 195B Typed by Cliatie Stoddard AC KOV'LEDGEMENTS The author would like to exprese his most sincere appreciation to Dr. E. C. Bubi, who by his guidance, help, and enthusiasm has made work on this project both an education and a pleasure. Especial thanks also o to Dr. Ian J. Tinsley, whose unfailing supply of timely suggestions, il1uminatin dis- cussions, and refreshing good humor was most generously shared. TABLE OF CONTENTS Chapter pase i INTRODUC T ION . i 2. LITERATURE STJRVEY . 5 3. PREPARATION AND IRRADIATION OF SAMPLES . 10 4. COLOR TESTS WITH THIOBARBITURIC ACID . 12 5. REAGENTS AND INSTRUMENTS . 15 6. GENERAL INFORMATION ON THE MEAT-TBA REACTION 17 Meat fractions and TBA reaction . 17 Spectral curves of meat-TBA piment solutions . 21 Autoc1avin of meat sampleß . ¿5 7. GENERAL INFORMATION ON THE GLYOXAL-TEA flc..tt'si.Lmr\?s1 L)i s S S S I S S S S ' Effect of pli on glyoxal-TBA reaction . 26 Glyoxal-barbituric acid reaction . 26 Barbituric acid reaction with beef . , 27 para-aminoacetophenone reaction with 1yoxal, malonaldehyde, and irradiated beef . 27 8. GLYOXAL-TBA AND :EAT-TBA PIGMENT PJI- FICATION e s .
    [Show full text]
  • WO 2016/103058 Al 30 June 2016 (30.06.2016) P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization I International Bureau (10) International Publication Number (43) International Publication Date WO 2016/103058 Al 30 June 2016 (30.06.2016) P O P C T (51) International Patent Classification: (74) Agent: KHURANA & KHURANA, ADVOCATES & IP C07D 317/68 (2006.01) C07C 45/56 (2006.01) ATTORNEYS; E-13, UPSIDC, Site-IV, Behind-Grand Venice, Kasna Road, UP, National Capital Region, Greater (21) International Application Number: Noida 201310 (IN). PCT/IB201 5/053 112 (81) Designated States (unless otherwise indicated, for every (22) International Filing Date: kind of national protection available): AE, AG, AL, AM, 29 April 2015 (29.04.2015) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (25) Filing Language: English BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (26) Publication Language: English HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (30) Priority Data: KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, 4124/MUM/2014 23 December 2014 (23. 12.2014) IN MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (71) Applicant: ANTHEA AROMATIC S PRIVATE LIM¬ SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, ITED [IN/IN]; R-81/82 TTC Industrial Area, Rabale Midc, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
    [Show full text]
  • STUDIES RELATED to the SYNTHESIS of Arylnaphthatrne LIGNANS
    1. STUDIES RELATED TO THE SYNTHESIS OF ARYLNAPHTHAtRNE LIGNANS A thesis presented by SUSAN MARY MELLOWS in partial fulfilment of the requirements for the degree of DOCTOR OF PHILOSOPHY of the UNIVERSITY OF LONDON Imperial College London S.W.7. October 1970. 2. Abstract This thesis is concerned with the synthesis o cyclolignans and in particular the synthesis of the pharmacologically active cyclolignan, podophyllotoxin. Existing syntheses of cyclolignans are reviewed. Various photochemical synthetic routes to the cyclolignans are proposed. One of these, the photoenolisation of o-benzylbenzaldehydes and subsequent Diels-Alder addition to the dienol of an appropriate dienophile has been investigated. Some general aspects of the photoenolisation reaction are discussed. Irradiation with ultra-violet light of the model compound o-tolualdehyde in the presence of dimethyl- acetylenedicarboxylate gave 2,3-dicarboxymethy1-1,4- -dihydro-l-naphthol. Cis-C1,C2-cis-C2,C3-l-tetralol- -2,3-dicarboxylic anhydride was formed by photoenolisation of o-tolualdehyde in the presence of maleic anhydride. Metal hydride reduction of the maleic anhydride adduct gave a mixture of cis-C1,C2-cis-C2,C3-2-carboxy-3-hydroxy- methyl-l-tetralo1-2,3'--lactone and cis-C1,C2-cis-C2,C3- 3-carboxy-2-hydroxymethyl-l-tetralo1-2',3-6'-lactone. gn acid catalysed rearrangement of the maleic anhydride adduct gave cis-C1,C2-cis-C2,C3-2,3-dicarboxy-l-tetralo1- 4-lactone which was reduced with diborane to cis-C1,C2- -cis-C2,C3-37carboxy-2-hydroxymethyl-l-tetralo1-2' ,3- - 3 • lactone. The synthesis of 6-(3,k,5-trimethoxybenzyl)piperonal is reported.
    [Show full text]
  • Piperine-Type Amides: Review of the Chemical and Biological Characteristics
    International Journal of Chemistry; Vol. 5, No. 3; 2013 ISSN 1916-9698 E-ISSN 1916-9701 Published by Canadian Center of Science and Education Piperine-Type Amides: Review of the Chemical and Biological Characteristics Simon Koma Okwute1 & Henry Omoregie Egharevba2 1 Department of Chemistry, Faculty of Science, University of Abuja, Gwagwalada, F. C. T., Nigeria 2 National Institute for Pharmaceutical Research and Development (NIPRD), Idu, Industrial Layout, Garki, Abuja, Nigeria Correspondence: Simon Koma Okwute, Department of Chemistry, Faculty of Science, University of Abuja, P.M.B. 117, Gwagwalada, F. C. T., Abuja, Nigeria. Tel: 234-803-595-3929. E-mail: [email protected] Received: June 13, 2013 Accepted: July 20, 2013 Online Published: July 28, 2013 doi:10.5539/ijc.v5n3p99 URL: http://dx.doi.org/10.5539/ijc.v5n3p99 Abstract A new group of alkaloids emerged in 1819 following the isolation of piperine from the fruits of Piper nigrum. Since then, a large number of these compounds now referred to as piperine-type alkaloids or alkamides or piperamides have been isolated commonly from species belonging to the genus piper (piperaceae) which have worldwide geographical distribution. As a result of the traditional uses of piper species as spices in foods and in phytomedicines globally a number of their extractives and indeed the constituent amides have been screened for pharmacological properties. The biogenesis of the amides has been investigated and a number of synthetic pathways have been developed to make them readily available for biological studies. It has now been established that piperine and its analogues are potential pesticides and possess a number of medicinal properties.
    [Show full text]
  • Chapter Five, Part D (Supervised Release)
    November 1, 2014 GUIDELINES MANUAL §2D1.1 PART D - OFFENSES INVOLVING DRUGS AND NARCO-TERRORISM Historical Note: Effective November 1, 1987. Amended effective November 1, 2007 (see Appendix C, amendment 711). 1. UNLAWFUL MANUFACTURING, IMPORTING, EXPORTING, TRAFFICKING, OR POSSESSION; CONTINUING CRIMINAL ENTERPRISE §2D1.1. Unlawful Manufacturing, Importing, Exporting, or Trafficking (Including Possession with Intent to Commit These Offenses); Attempt or Conspiracy (a) Base Offense Level (Apply the greatest): (1) 43, if the defendant is convicted under 21 U.S.C. § 841(b)(1)(A), (b)(1)(B), or (b)(1)(C), or 21 U.S.C. § 960(b)(1), (b)(2), or (b)(3), and the offense of conviction establishes that death or serious bodily injury resulted from the use of the substance and that the defendant committed the offense after one or more prior convictions for a similar offense; or (2) 38, if the defendant is convicted under 21 U.S.C. § 841(b)(1)(A), (b)(1)(B), or (b)(1)(C), or 21 U.S.C. § 960(b)(1), (b)(2), or (b)(3), and the offense of conviction establishes that death or serious bodily injury resulted from the use of the substance; or (3) 30, if the defendant is convicted under 21 U.S.C. § 841(b)(1)(E) or 21 U.S.C. § 960(b)(5), and the offense of conviction establishes that death or serious bodily injury resulted from the use of the substance and that the defendant committed the offense after one or more prior convictions for a similar offense; or (4) 26, if the defendant is convicted under 21 U.S.C.
    [Show full text]
  • Precursors and Chemicals Frequently Used in the Illicit Manufacture Of
    INTERNATIONAL NARCOTICS CONTROL BOARD 2005 Precursors and chemicals frequently used in the illicit manufacture of narcotic drugs and psychotropic substances EMBARGO Observe release date: Not to be published or broadcast before Wednesday, 1 March 2006, at 0001 hours (GMT) CAUTION UNITED NATIONS Reports published by the International Narcotics Control Board in 2005 The Report of the International Narcotics Control Board for 2005 (E/INCB/2005/1) is supplemented by the following technical reports: Narcotic Drugs: Estimated World Requirements for 2006; Statistics for 2004 (E/INCB/2005/2) Psychotropic Substances: Statistics for 2004; Assessments of Medical and Scientific Requirements for Substances in Schedules II, III and IV of the Convention on Psychotropic Substances of 1971 (E/INCB/2005/3) Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances: Report of the International Narcotics Control Board for 2005 on the Implementation of Article 12 of the United Nations Convention against Illicit Traffic in Narcotic Drugs and Psychotropic Substances of 1988 (E/INCB/2005/4) The updated lists of substances under international control, comprising narcotic drugs, psychotropic substances and substances frequently used in the illicit manufacture of narcotic drugs and psychotropic substances, are contained in the latest editions of the annexes to the statistical forms (“Yellow List”, “Green List” and “Red List”), which are also issued by the Board. Contacting the International Narcotics Control Board The secretariat of the Board may be reached at the following address: Vienna International Centre Room E-1339 P.O. Box 500 1400 Vienna Austria In addition, the following may be used to contact the secretariat: Telephone: + (43-1) 26060 Telex: 135 612 Fax: + (43-1) 26060-5867 or 26060-5868 Cables: unations vienna E-mail: [email protected] The text of the present report is also available on the website of the Board (http://www.incb.org).
    [Show full text]
  • Oxidation of Aldehydes to Nitriles with an Oxoammonium Salt: Preparation of Piperonylonitrile
    Oxidation of Aldehydes to Nitriles with an Oxoammonium Salt: Preparation of Piperonylonitrile Nathaniel D. Kaetzel,† Kyle M. Lambert,1*‡ and Christopher B. Kelly2,3*† † Department of Chemistry, Virginia Commonwealth University, 1001 West Main Street, P.O. Box 842006, Richmond, Virginia 23284 ‡ Department of Chemistry and Biochemistry, Old Dominion University, 4541 Hampton Boulevard, Norfolk, Virginia 23529, United States Checked by Charis A. Roberts and Richmond Sarpong Procedure (Note 1) Piperonylonitrile (4). A 500-mL single-necked, round-bottomed flask (24/40) equipped with a Teflon-coated, oval, magnetic stir bar (2 cm x 2 cm x 4 cm) and is left open to the air. The flask is charged with piperonal (1) (10.51 g, 70 mmol, 1 equiv) and dichloromethane (140 mL) (Notes 2 and 3). The flask is placed in a room temperature (26 °C) water bath, magnetic stirring is commenced (Note 4), and the contents of the flask are allowed to stir for 2 min to allow for complete dissolution. Pyridine (6.2 mL, 6.1 g, 77 mmol, 1.1 equiv) (Note 2) is added, followed by the addition HMDS (36.7 mL, 28.2 g, 175 mmol, 2.5 equiv) (Note 2) (Note 5). Org. Synth. 2020, 97, 294-313 294 Published on the Web 10/13/2020 DOI: 10.15227/orgsyn.097.0294 Ó 2020 Organic Syntheses, Inc. Figure 1. Progression and observed color change of reaction; (a) Upon initial addition of 2, (b) Upon removal of funnel and addition of temperature probe, (c) 15 Minutes after addition of 2, (d) 30 Minutes after addition of 2, (e) 60 Minutes after addition of 2, (f) Upon completion of reaction 120 minutes after addition of 2 (photos provided by submitters) The solution is left to stir at room temperature (26 °C) for five min, at which point the oxoammonium salt (2) (52.5 g, 175 mmol, 2.5 equiv) (Note 6) is added to the flask via a plastic powder funnel (OD: 7.5 cm, ID: 1.6 cm) gradually over a two-minute period (Figure 1A).
    [Show full text]
  • Piper Nigrum CYP719A37 Catalyzes the Decisive Methylenedioxy Bridge Formation in Piperine Biosynthesis
    plants Article Piper nigrum CYP719A37 Catalyzes the Decisive Methylenedioxy Bridge Formation in Piperine Biosynthesis Arianne Schnabel 1 , Fernando Cotinguiba 2 , Benedikt Athmer 1 and Thomas Vogt 1,* 1 Leibniz Institute of Plant Biochemistry, Department Cell and Metabolic Biology, Weinberg 3, D-06120 Halle (Saale), Germany; [email protected] (A.S.); [email protected] (B.A.) 2 Instituto de Pesquisas de Produtos Naturais (IPPN), Universidade Federal do Rio de Janeiro (UFRJ), Avenida Carlos Chagas Filho, 373, 21941-902 Rio de Janeiro/RJ, Brazil; [email protected] * Correspondence: [email protected] Abstract: Black pepper (Piper nigrum) is among the world’s most popular spices. Its pungent principle, piperine, has already been identified 200 years ago, yet the biosynthesis of piperine in black pepper remains largely enigmatic. In this report we analyzed the characteristic methylenedioxy bridge formation of the aromatic part of piperine by a combination of RNA-sequencing, functional expression in yeast, and LC-MS based analysis of substrate and product profiles. We identified a single cytochrome P450 transcript, specifically expressed in black pepper immature fruits. The corresponding gene was functionally expressed in yeast (Saccharomyces cerevisiae) and characterized for substrate specificity with a series of putative aromatic precursors with an aromatic vanilloid structure. Methylenedioxy bridge formation was only detected when feruperic acid (5-(4-hydroxy- 3-methoxyphenyl)-2,4-pentadienoic acid) was used as a substrate, and the corresponding product was identified as piperic acid. Two alternative precursors, ferulic acid and feruperine, were not accepted. Our data provide experimental evidence that formation of the piperine methylenedioxy bridge takes place in young black pepper fruits after a currently hypothetical chain elongation of ferulic acid and before the formation of the amide bond.
    [Show full text]
  • Skin Reaction Induced by Aldehydes for Food Flavoring Agents
    Journal of Health Science, 47(3) 327–329 (2001) 327 Skin Reaction Induced by to assess whether these aldehydes induce allergic re- action including atopic dermatitis. The present study Aldehydes for Food Flavoring describes skin reactions in guinea pigs induced by Agents aldehydes for food flavoring agents. Kazuhito Watanabe, Midori Matsuda, MATERIALS AND METHODS Shizuka Furuhashi, Toshiyuki Kimura, Tamihide Matsunaga, and Ikuo Yamamoto* Chemicals and Animals —–— p-Anisaldehyde, ci- Department of Hygienic Chemistry, Faculty of Pharmaceutical tral, ethylvanillin, n-octanal, piperonal and vanillin Sciences, Hokuriku University, Kanazawa 920–1181, Japan were obtained from Wako Pure Chem. Ind. (Osaka, (Received February 1, 2001; Accepted February 22, 2001) Japan); benzaldehyde, furfural and l-perillaldehyde were purchased from Nacalai Tesque (Kyoto, Japan), Guinea pigs were sensitized intracutaneously for Tokyo Kasei Kogyo Co. (Tokyo, Japan) and Aldrich 7 days (0.1 ml of 1% aldehyde solution/day) with nine Chem. Co., Inc. (U.S.A), respectively. Other chemi- aldehydes (p-anisaldehyde, benzaldehyde, citral, cals used were obtained from Wako Pure Chem. Ind. ethylvanillin, furfural, n-octanal, l-perillaldehyde, pip- (Osaka, Japan). Hartley male guinea pigs (8 weeks eronal and vanillin) which are used as the food flavor- old, 300–400 g) were purchased from Sankyo Lab. ing agents. Three weeks later, each aldehyde was in- (Toyama, Japan) and were given water and food ad jected by different concentrations (0.25–1.0%). Skin libitum. reactions were observed 24 hr after the injection of Sensitization and Skin Reaction —–— The animals the aldehydes. All aldehydes tested exhibited a posi- were sensitized by the method described previously, tive skin reaction, indicating that these aldehydes are 5,6) capable of inducing an allergic reaction.
    [Show full text]
  • Multilingual Dictionary of Precursors and Chemicals Frequently Used In
    Vienna International Centre, PO Box 500, 1400 Vienna, Austria AND RUSSIAN) (ARABIC, CHINESE, ENGLISH, FRENCH, SPANISH CONTROL UNDER INTERNATIONAL AND PSYCHOTROPIC SUBSTANCES DRUGS OF NARCOTIC MANUFACTURE THE IILICIT USED IN AND CHEMICALS FREQUENTLY OF PRECURSORS DICTIONARY MULTILINGUAL Tel.: (+43-1) 26060-0, Fax: (+43-1) 26060-5866, www.unodc.org USD 65 United Nations publication ISBN 978-92-1-048128-1 Printed in Austria Sales No. M.09.XI.14 V.09-83217—August*0983217* 2009—440 UNITED NATIONS New York, 2009 Acknowledgements This Multilingual Dictionary of Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances under International Control, was produced in the Laboratory and Scientific Section (LSS) of UNODC. The preparation and coordination was done by Anna LLoberas Blanch, Iphigenia Naidis and Barbara Remberg, staff of UNODC LSS (headed by Justice Tettey). The LSS is grateful to all other UNODC colleagues who contributed to this publication. ST/NAR/1A* UNITED NATIONS PUBLICATION Sales No. M.09.XI.14 ISBN 978-92-1-048128-1 * This publication is complementary to Multilingual Dictionary of Narcotic Drugs and Psychotropic Substances under International Control, ST/NAR/1. This publication has not been formally edited. T A B L E O F C O N T E N T S Page PREFACE ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ v EXPLANATORY NOTES ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ vii Terminology ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
    [Show full text]