DOCSLIB.ORG

Direct and Facile Synthesis of Acyl Isothiocyanates from Carboxylic Acids Using Trichloroisocyanuric Acid/Triphenylphosphine System

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Direct and Facile Synthesis of Acyl Isothiocyanates from Carboxylic Acids Using Trichloroisocyanuric Acid/Triphenylphosphine System CROATICA CHEMICA ACTA CCACAA, ISSN 0011-1643, e-ISSN 1334-417X Croat. Chem. Acta 87 (3) (2014) 201–206. http://dx.doi.org/10.5562/cca2381 Original Scientific Article Direct and Facile Synthesis of Acyl Isothiocyanates from Carboxylic Acids Using Trichloroisocyanuric Acid/Triphenylphosphine System Najmeh Entezari, Batool Akhlaghinia,* and Hamed Rouhi-Saadabad Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad 9177948974, Iran RECEIVED NOVEMBER 7, 2013; REVISED JUNE 3, 2014; ACCEPTED AUGUST 27, 2014 Abstract. A mild, efficient, and practical method for one-step synthesis of alkanoyl and aroyl isothiocyanates from carboxylic acids using a safe and inexpensive mixed reagent, trichloroisocyanuric acid/triphenyl- phosphine is described at room temperature. Availability of the reagents and easy workup of the reaction make this method attractive for organic chemists. Keywords: acyl isothiocyanates, carboxylic acids, trichloroisocyanuric acid (TCCA), triphenylphosphine (TPP), potassium thiocyanate INTRODUCTION azides from carboxylic acids and sulfonic acids under mild and neutral reaction conditions by using the above Acyl isothiocyanates have found wide application in the mentioned mixed reagents.19–21 Herein we wish to report synthesis of various acyclic and heterocyclic compounds, a simplified, rapid and one-step method for the conver- including those possessing biological activity.1–3 sion of carboxylic acids to acyl isothiocyanates in the The methods of preparation of isothiocyanates are presence of TPP/TCCA as a mild, efficient and inex- limited.2 many methods have been described for the pensive reagent system at room temperature. 4–14 preparation of acyl isothiocyanates. which are main- ly based on the reaction of acyl halides with thiocyanate EXPERIMENTAL ion.2,6 Acyl halides are not always easy to access or store. As acyl halides are highly sensitive to moisture General and require care in handling, these methods need to anhydrous conditions and long reaction time.6 The reac- The products were purified by column chromatography. tion of carbonimidoyl dichloride with metal thiocyanate The purity determinations of the products were accom- is also another reported method of preparation of acyl plished by TLC on silica gel polygram STL G/UV 254 isothiocyanates, but the starting material is not easily plates. The melting points of products were determined available and the yield of the reaction is too low.15 with an Electrothermal Type 9100 melting point appa- There are few reports on the direct conversion of car- ratus. The FT-IR spectra were recorded on an Avatar boxylic acids to acyl isothiocyanates using acid activa- 370 FT-IR Therma Nicolet spectrometer. The NMR tors such as Ph3P(SCN)2 (Ref. 16) and PO(NCS)3 (Ref. spectra were provided on Brucker Avance 100 and 400 17). Preparation of the reagents in these methods suffers MHz instruments in CDCl3 and DMSO. Mass spectra from difficult procedures and the reactions take long were recorded with a CH7A Varianmat Bremem in- time. Conversion of trialkylsilyl carboxylates to acyl strument at 70 eV; in m/z (rel %). Elemental analyses isothiocyanates was also reported by using Ph3P(SCN)2 were performed using an Elementar, Vario EL III and (Ref. 18). This methodology cannot be considered as a Thermofinnigan Flash EA 1112 Series instrument. Most direct preparation of acyl isothiocyanates and also needs of the products were known compounds and character- initial preparation of reagents. ized by the IR and comparison of their melting points By considering the activity of trichloroisocyanuric with authentic samples. The structure of unknown prod- acid (TCCA) and N-chlorobenzotriazole (NCBT) to- ucts and some selected known products was further wards triphenylphosphine, recently we reported direct confirmed by 1H NMR, 13C NMR spectroscopy, mass preparation of acyl azides, esters, thioesters and sulfonyl spectrometry and elemental analysis. * Author to whom correspondence should be addressed. (E-mail: [email protected]) 202 N. Entezari et al., Direct Synthesis of Acyl Isothiocyanates from Carboxylic Acids Preparation of Benzoyl Isothiocyanate from Benzoic 1012, 861, 840, 738, 666, 532; MS m/z: 197 (M+, 2.5 %); Acid 138 (M+–NCS, 100 %); 110 (M+–CONCS, 92.5 %); 75 (Ph, 95 %). To a cold solution of triphenylphosphine (0.262 g, 1 mmol) in toluene (3 mL), trichloroisocyanuric acid (0.069 g, 4-Bromobenzoyl Isothiocyanate (Table 2, entry 7) 0.3 mmol) was added with continuous stirring. Benzoic Solid; m.p. 53–55 °C (Ref. 26) 54–55 °C; IR (KBr) –1 acid (0.097g, 0.8 mmol) was added and stirring was ῡmax /cm : 3088, 2197, 2039, 1985 (N=C=S), 1687 continued for 15 min. Potassium thiocyanate (0.193 g, (C=O), 1587, 1482, 1397, 1269, 1172, 1100, 1066, 2 mmol) was added and the temperature was raised up 1010, 860, 837, 734, 665, 510, 459; 1H NMR (400 to room temperature. Stirring was continued for 40 min MHz, CDCl3) δ/ppm: 7.67 (d, 2H, J = 8.8 Hz, ArH), at room temperature. The progress of the reaction was 7.94 (d, 2H, J = 8.8 Hz, ArH); 13C NMR (100 MHz, followed by TLC. Upon completion of the reaction, CDCl3) δ/ppm: 161.4 (C=O), 149.1 (N=C=S), 132.4, the concentrated residue passed through a short silica- 131.8, 130.7, 129.8, 129.7; MS m/z: 243 (M++2, gel column using n-hexane / ethyl acetate mixture (vol. 25 %); 241 (M+, 25 %); 183 (M+–NCS, 100 %); 155 ratio: 60:1) as the eluent. Benzoyl isothiocyanate was (M+–CONCS, 85 %). obtained with 95 % yield after removing the solvent 4-Methylbenzoyl Isothiocyanate (Table 2, entry 8) under reduced pressure. 27 –1 Oil; IR (neat) ῡmax /cm : 3043, 2986, 2913, 2847, Benzoyl Isothiocyanate (Table 2, entry1) 1974 (N=C=S), 1931, 1696 (C=O), 1607, 1511, 1446, 22 –1 Oil; IR (neat) ῡmax /cm : 2964, 2932, 2876, 1978 1405, 1256, 1175, 1082, 861, 785, 747, 677, 597. (N=C=S), 1694 (C=O), 1597, 1451, 1253, 1239, 1175, 3,5-Dimethylbenzoyl Isothiocyanate (Table 2, entry 9) 1083, 1067, 855, 693, 670, 648. 6 –1 Oil; IR (neat) ῡmax /cm : 3015, 2925, 2864, 1973 4-Nitrobenzoyl Isothiocyanate (Table 2, entry2) (N=C=S), 1697 (C=O), 1606, 1453, 1379, 1301, 1182, Solid; m.p. 90–92 °C (Ref. 13) 92–93 °C; IR (KBr) 1164, 1100, 937, 865, 762, 735, 669, 547, 449; 1 HNMR –1 ῡmax /cm : 3268, 3096, 3072, 3039, 1993 (N=C=S), (400 MHz, CDCl3) δ/ppm: 2.41 (s, 6H, 2CH3), 7.30 (d, 1956, 1690 (C=O), 1601, 1523, 1346, 1321, 1270, 1103, 1H, J=10 Hz, ArH), 7.69 (s, 2H, ArH); 13C NMR (100 + 874, 839, 709, 669, 510; MS m/z: 206 (M , 5 %); 149 MHz, CDCl3) δ/ppm: 161.9 (C=O), 147.40 (N=C=S), (M+–NCS, 72.5 %); 121 (M+–CONCS, 7.5 %); 75 (Ph, 138.8, 138.3, 136.9, 136.2, 133.7, 130.7, 128.3, 126.2, 95 %); Anal. Calcd. mass fractions of elements, w/%, for 125.2, 21.3, 21.2. C H N O S (M = 208.19) are: C 46.15, H 1.94, N 13.46, 8 4 2 3 r 4-Methoxybenzoyl isothiocyanate (Table 2, entry 10) S 15.40; Found: C 46.36, H 1.66, N 14.08, S 16.05. 4 –1 Oil; IR (neat) ῡmax /cm : 2961, 2932, 2839, 2160, 1973 3-Nitrobenzoyl Isothiocyanate (Table 2, entry 3) (N=C=S), 1930, 1690 (C=O), 1603, 1577, 1506, 1423, Solid; m.p. 94–95 °C (Ref. 23) 95–96 °C; IR (KBr) 1330, 1250, 1164, 1085, 1023, 863, 785, 750, 681, 599. ῡ /cm–1: 3370, 3244, 3092, 3080, 2929, 2855, 1991 max 4-(Isothiocyanatocarbonyl) phenyl acetate (Table 2, (N=C=S), 1723, 1684 (C=O), 1613, 1537, 1525, 1351, entry 11) 1290, 1265, 1127, 927, 820, 709, 690; MS m/z: 206 Oil; IR(neat) ῡ /cm–1: 2956, 2916, 2848, 1981 (M+, 15 %); 149 (M+–NCS, 100 %); 121 (M+–CONCS, max (N=C=S), 1936, 1774 (C=O), 1703, 1598, 1503, 1417, 25 %); 75 (Ph, 80 %); Anal. Calcd. mass fractions 1370, 1249, 1198, 1161, 1017, 910, 882, 850, 681, 645, of elements, w/%, for C H N O S (M = 208.19) are: 8 4 2 3 r 592; 1H NMR (400 MHz, DMSO-d6) δ/ppm: 2.26 (s, C 46.15, H 1.94, N 13.46, S 15.40; Found: C 46.28, 3H, Me), 7.22 (d, 2H, J = 8.4 Hz, ArH), 7.95 (d, 2H, J = H 1.62, N 13.40, S 15.55. 8.4 Hz, ArH); 13C NMR (100 MHz, DMSO-d6) δ/ppm: 3,4-Dichlorobenzoyl Isothiocyanate (Table 2, entry 4) 161.9 (O-C=O), 161.4 (N-C=O), 148.2 (N=C=S), 133.2, 24 –1 + Oil; IR (neat) ῡmax /cm : 3362, 3166, 3084, 3060, 132.4, 132.2, 129.9, 22.3; MS m/z: 221 (M , 5 %); 163 2018, 1955 (N=C=S), 1693 (C=O), 1658, 1583, 1458, (M+–NCS, 8 %); 104 (PhCO, 100 %); Anal. Calcd. mass 1383, 1266, 1232, 1106, 1030, 898, 837, 764, 734, 706, fractions of elements, w/%, for C10H7NO3S (Mr = 681, 547. 221.23) are: C 54.29, H 3.19, N 6.33, S 14.49; Found: C 54.08, H 3.29, N 6.48, S 14.92. 2-Chlorobenzoyl Isothiocyanate (Table 2, entry 5) 4 –1 Oil; IR (neat) ῡmax /cm : 3076, 1981 (N=C=S), 1948, 4-Acetamidobenzoyl Isothiocyanate (Table 2, entry 12) 28 –1 1790 (C=O), 1728, 1691, 1590, 1473, 1439, 1319, 1203, Oil; IR (neat) ῡmax /cm : 3460, 3264, 3182, 3096, 1132, 1077, 932, 997, 775, 742, 620, 477. 2953, 2921, 2851, 1989 (N=C=S), 1697 (C=O), 1594, 1536, 1413, 1315, 1253, 1170, 1021, 955, 869, 751, 677.
Load more

Recommended publications
  • Heats of Formation of Certain Nickel-Pyridine Complex Salts
    HEATS OF FORFATION OF CERTAIN NICKEL-PYRIDINE COLPLEX SALTS DAVID CLAIR BUSH A THESIS submitted to OREGON STATE COLLEGE in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE June l9O [4CKNOWLEDGMENT The writer wishes to acknowledge his indebtedness and gratitude to Dr. [4. V. Logan for his help and encour- agement during this investigation. The writer also wishes to express his appreciation to Dr. E. C. Gilbert for helpful suggestions on the con- struction of the calortheter, and to Lee F. Tiller for his excellent drafting and photostating of the figures and graphs. APPROVED: In Charge of ?ajor Head of Department of Chemistry Chairrian of School Graduate Comrittee Dean of Graduate School Date thesis is presented /11 ' Typed by Norma Bush TABLE OF CONTENTS HISTORICAL BACKGROUND i INTRODUCTION 2 EXPERIMENTAL 5 Preparation of the Compounds 5 Analyses of the Compounds 7 The Calorimeter Determination of the Heat Capacity 19 Determination of the Heat of Formation 22 DISCUSSION 39 41 LITERATURE CITED 42 TABLES I Analyses of the Compounds 8 II Heat Capacity of the Calorimeter 23 III Heat of Reaction of Pyridine 26 IV Sample Run and Calculation 27 V Heat of Reaction of Nickel Cyanate 30 VI Heat of Reaction of Nickel Thiocyanate 31 VII Heat of Reaction of Hexapyridinated Nickel Cyanate 32 VIII Heat of Reaction of Tetrapyridinated Nickel Thiocyanate 33 IX Heat of Formation of the Pyridine Complexes 34 FI GURES i The Calorimeter 10 2 Sample Ijector (solids) 14 2A Sample Ejector (liquids) 15 3 Heater Circuit Wiring Diagram 17 4 heat Capacity of the Calorimeter 24 5 Heat of Reaction of Pyridine 28 6 Heat of Reaction of Hexapyridinated Nickel Cyanate 35 7 Heat of Reaction of Tetrapyridinated Nickel Thiocyanate 36 8 Heat of Reaction of Nickel Cyanate 37 9 Heat of Reaction of Nickel Thiocyanate 38 HEATS OF FOW ATION OF CERTAIN NICKEL-PYRIDINE COMPLEX SALTS HISTORICAL BACKGROUND Compounds of pyridine with inorganic salts have been prepared since 1970.
    [Show full text]
  • United States Patent Office Patented Jan
    3,071,593 United States Patent Office Patented Jan. 1, 1963 2 3,071,593 O PREPARATION OF AELKENE SULFES Paul F. Warner, Philips, Tex., assignor to Philips Petroleum Company, a corporation of Delaware wherein each R is selected from the group consisting of No Drawing. Filed July 27, 1959, Ser. No. 829,518 5 hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl 8 Claims. (C. 260-327) groups having 1 to 8 carbon atoms, the combined R groups having up to 12 carbon atoms. Examples of Suit This invention relates to a method of preparing alkene able compounds are ethylene oxide, propylene oxide, iso sulfides. Another aspect relates to a method of convert butylene oxide, a-amylene oxide, styrene oxide, isopropyl ing an alkene oxide to the corresponding sulfide at rela O ethylene oxide, methylethylethylene oxide, 3-phenyl-1, tively high yields without refrigeration. 2-propylene oxide, (3-methylphenyl) ethylene oxide, By the term "alkene sulfide' as used in this specifica cyclohexylethylene oxide, 1-phenyl-3,4-epoxyhexane, and tion and in the claims, I mean to include not only un the like. substituted alkene sulfides such as ethylene sulfide, propyl The salts of thiocyanic acid which I prefer to use are ene sulfide, isobutylene sulfide, and the like, but also 5 the salts of the alkali metals or ammonium. I especially hydrocarbon-substituted alkene sulfides such as styrene prefer ammonium thiocyanate, sodium thiocyanate, and oxide, and in general all compounds conforming to the potassium thiocyanate. These compounds can be reacted formula with ethylene oxide in a cycloparaffin diluent to produce 20 substantial yields of ethylene sulfide and with little or S no polymer formation.
    [Show full text]
  • House Fly Attractants and Arrestante: Screening of Chemicals Possessing Cyanide, Thiocyanate, Or Isothiocyanate Radicals
    House Fly Attractants and Arrestante: Screening of Chemicals Possessing Cyanide, Thiocyanate, or Isothiocyanate Radicals Agriculture Handbook No. 403 Agricultural Research Service UNITED STATES DEPARTMENT OF AGRICULTURE Contents Page Methods 1 Results and discussion 3 Thiocyanic acid esters 8 Straight-chain nitriles 10 Propionitrile derivatives 10 Conclusions 24 Summary 25 Literature cited 26 This publication reports research involving pesticides. It does not contain recommendations for their use, nor does it imply that the uses discussed here have been registered. All uses of pesticides must be registered by appropriate State and Federal agencies before they can be recommended. CAUTION: Pesticides can be injurious to humans, domestic animals, desirable plants, and fish or other wildlife—if they are not handled or applied properly. Use all pesticides selectively and carefully. Follow recommended practices for the disposal of surplus pesticides and pesticide containers. ¿/áepé4áaUÁí^a¡eé —' ■ -"" TMK LABIL Mention of a proprietary product in this publication does not constitute a guarantee or warranty by the U.S. Department of Agriculture over other products not mentioned. Washington, D.C. Issued July 1971 For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 - Price 25 cents House Fly Attractants and Arrestants: Screening of Chemicals Possessing Cyanide, Thiocyanate, or Isothiocyanate Radicals BY M. S. MAYER, Entomology Research Division, Agricultural Research Service ^ Few chemicals possessing cyanide (-CN), thio- cyanate was slightly attractive to Musca domes- eyanate (-SCN), or isothiocyanate (~NCS) radi- tica, but it was considered to be one of the better cals have been tested as attractants for the house repellents for Phormia regina (Meigen).
    [Show full text]
  • Thiocyanate Pyridine Complexes
    W&M ScholarWorks Undergraduate Honors Theses Theses, Dissertations, & Master Projects 5-2017 Structural Comparison of Copper(II) Thiocyanate Pyridine Complexes Joseph V. Handy College of WIlliam & Mary Follow this and additional works at: https://scholarworks.wm.edu/honorstheses Part of the Inorganic Chemistry Commons Recommended Citation Handy, Joseph V., "Structural Comparison of Copper(II) Thiocyanate Pyridine Complexes" (2017). Undergraduate Honors Theses. Paper 1100. https://scholarworks.wm.edu/honorstheses/1100 This Honors Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Undergraduate Honors Theses by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. Structural Comparison of Copper(II) Thiocyanate Pyridine Complexes A thesis submitted in partial fulfillment of the requirement for the degree of Bachelor of Science in Chemistry from The College of William & Mary by Joseph Viau Handy Accepted for ____________________________ ________________________________ Professor Robert D. Pike ________________________________ Professor Deborah C. Bebout ________________________________ Professor David F. Grandis ________________________________ Professor William R. McNamara Williamsburg, VA May 3, 2017 1 Table of Contents Table of Contents…………………………………………………...……………………………2 List of Figures, Tables, and Charts………………………………………...…………………...4 Acknowledgements….…………………...………………………………………………………6
    [Show full text]
  • On the Effects of Urea on the Molecular Structure and Activity of Various
    The Journal of Biochemistry, Vol. 58, No. 1, 1965 Effects of Urea on the Activity and Structure of Yeast Alcohol Dehydrogenase By TAKAHISA OHTA* and YASUYUEI OGURA (From the Department of Biophysics and Biochemistry, Faculty of Science, University of Tokyo, Bunkyo-ku, Tokyo) (Received for publication, March 29, 1965) There have been many reports (1-8) on (9) and K lot z (10). However, to interprete the effects of urea on the molecular structure the mechanism of inhibition by urea on enzyme and activity of various enzymes. Most reactions, further investigations are necessary enzymes (1-4) are known to be inhibited by since few have covered both kinetics of the en low concentrations of urea which do not zymatic reaction and physicochemical analysis denature their protein. The mode of inhibi of the structural changes of the enzyme protein. tion of urea on various enzyme reactions has In this paper, the effects of urea upon yeast been studied kinetically by R a j a g o p a l a n, alcohol dehydrogenase [EC 1. 1. 1. 1, Alcohol: Fridovich and Handler (3) and also NAD oxidoreductase (yeast)] have been studi by Chase's group (6-8) using rather low ed, focusing attention on the relationship be concentrations of urea. The inhibition by tween the structure of the enzyme molecule urea of various enzymes, such as xanthine and its catalytic activity. oxidase [EC 1.2.3.2], muscle lactate dehydro EXPERIMENTAL genase [EC 1. 1. 1. 27] (3) and kidney aldose mutarotase [EC 5.1.3.3] (6) has been reported Materials-Yeast alcohol dehydrogenase was prepar to be reversible and competitive for the sub ed from fresh baker's yeast* by the following pro strate.
    [Show full text]
  • Silver-Based Monomer and Coordination
    Silver-based monomer and coordination polymer with organic thiocyanate ligand: Structural, computational and antiproliferative activity study Nenad Filipović, Predrag Ristić, Goran Janjić, Olivera Klisurić, Adrián Puerta, José Padrón, Morgan Donnard, Mihaela Gulea, Tamara Todorović To cite this version: Nenad Filipović, Predrag Ristić, Goran Janjić, Olivera Klisurić, Adrián Puerta, et al.. Silver- based monomer and coordination polymer with organic thiocyanate ligand: Structural, com- putational and antiproliferative activity study. Polyhedron, Elsevier, 2019, 173, pp.114132. 10.1016/j.poly.2019.114132. hal-02319545 HAL Id: hal-02319545 https://hal.archives-ouvertes.fr/hal-02319545 Submitted on 5 Nov 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Graphical Abstract - Pictogram (for review) Click here to download Graphical Abstract - Pictogram (for review) GraphicalAbstract-pictogram.tif Graphical Abstract - Synopsis (for review) Click here to download Graphical Abstract - Synopsis (for review) Graphical-Abstract-with-Synopsis.docx Graphical Abstract Analyzed structures of silver-based monomer and coordination polymer with organic thiocyanate represent an example where the nature of (non)coordinated ions were found to have the profound influence on coordination mode of the ligand and consequently crystal packing. The monomer showed an excellent antiproliferative activity in tested human tumor cell lines.
    [Show full text]
  • Synthesis and Transformations of 2-Thiocarbohydrates : a Practical
    Institut für Chemie Organische Chemie Synthesis and Transformations of 2-Thiocarbohydrates: A Practical Approach for Functionalization of Thiosugars Dissertation zur Erlangung des akademischen Grades "doctor rerum naturalium" (Dr. rer. nat.) in der Wissenschaftsdisziplin "Organische Chemie" eingereicht an der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Potsdam von Prashant Pavashe From Ahmednagar, India Potsdam, im Januar 2017 Published online at the Institutional Repository of the University of Potsdam: URN urn:nbn:de:kobv:517-opus4-397739 http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-397739 Publication based on this thesis ‘‘Synthesis of 2-Thiocarbohydrates and Their binding to concanavalin A’’ Prashant Pavashe, Elangovan Elamparuthi, Cornelia Hettrich, Heiko M. Möller, Torsten Linker, J. Org. Chem. 2016, 81, 8595–8603. Table of contents Table of contents Table of contents………….................................................................................................. i Acknowledgements………….............................................................................................. iii Abstract…………................................................................................................................. v Zusammenfassung…………............................................................................................... viii 1. Introduction………….............................................................................................. 1 2. Research background…………...............................................................................
    [Show full text]
  • Biomarkers of Tuber Intake Xiaomin Zhou1* , Qian Gao1, Giulia Praticò1,2, Jie Chen3 and Lars Ove Dragsted1
    Zhou et al. Genes & Nutrition (2019) 14:9 https://doi.org/10.1186/s12263-019-0631-0 REVIEW Open Access Biomarkers of tuber intake Xiaomin Zhou1* , Qian Gao1, Giulia Praticò1,2, Jie Chen3 and Lars Ove Dragsted1 Abstract Tubers are important crops as well as staple foods in human nutrition. Among tubers, the potato in particular has been investigated for its health effects. However, except for its contribution to energy and effects related to resistant starch, the role of potatoes and other tubers in human health is still debated. In order to establish firm evidence for the health effects of dietary tubers and processed tuber products, it is essential to assess total intake accurately. The dietary assessment in most studies relies mainly on self-reporting and may give imprecise quantitative information on dietary intakes. Biomarkers of food intake (BFIs) are useful objective means to assess intake of specific foods or may be used as an additional measure to calibrate the measurement error in dietary reports. Here, intake biomarkers for common tubers, including potatoes and heated potato products, sweet potato, cassava, yam, and Jerusalem artichoke, are reviewed according to the biomarker of food intake reviews (BFIRev) standardized protocols for review and validation. Candidate BFIs for heated potato product include α-chaconine, α- solanine, and solanidine; less evidence is available to indicate peonidin 3-caffeoylsophoroside-5-glucoside and cyanidin 3-caffeoylsophoroside-5-glucoside as putative biomarkers having high potential specificity for purple sweet potato intake; linamarin may in addition be considered as a putative BFI for cassava. Other tubers also contain toxic glycosides or common contaminants as characteristic components but their putative use as intake biomarkers is not well documented.
    [Show full text]
  • Self-Assembled Thin Films of Thiocyanate and Selenocyanate Bithiophenes
    Lakehead University Knowledge Commons,http://knowledgecommons.lakeheadu.ca Electronic Theses and Dissertations Electronic Theses and Dissertations from 2009 2015-06-15 Self-assembled thin films of thiocyanate and selenocyanate bithiophenes Kelly, Kaitlyn T. http://knowledgecommons.lakeheadu.ca/handle/2453/638 Downloaded from Lakehead University, KnowledgeCommons Self-assembled thin films of thiocyanate and selenocyanate bithiophenes A Thesis Presented to the Department of Chemistry Of Lakehead University By Kaitlyn T. Kelly In partial fulfillment of requirements for the degree of Master of Chemistry February 5th, 2015 Official Signature of Supervisor Page i Abstract Presented herein is the organic synthesis and thin film (TF) assembly of six alkyl-substituted thiocyante and selenocyante bithiophene molecules: NCSe-T2-Hx, NCS-T2-Hx, NCS-Hx-T2-Hx, NCSe- Hx-T2-Hx, NCS-Hx-T2-Hx-SCN and NCSe-Hx-T2-Hx-SeCN. TFs assembled from these thio and selenocyanates were characterized by six different techniques: electrochemical capacitance (Cp) measurements, scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Cp experiments were used to confirm the development of TFs on an amorphous Au surface using ethanol or hexanes as a reaction solvent. A sputtered Au surface was observed by SEM/EDX to be an inappropriate surface for TF assembly. TFs assembled onto epitaxially grown Au were characterized by multiple techniques. Large crystallites were observed on TFs assembled from NCSe-T2-Hx and NCSe-Hx-T2-Hx-SeCN. Chemical maps of these crystallites were obtained through SEM/EDX.
    [Show full text]
  • Kinetics of Decomposition of Thiocyanate in Natural Aquatic Systems Irina Kurashova,† Itay Halevy,‡ and Alexey Kamyshny, Jr.*,†
    Article Cite This: Environ. Sci. Technol. 2018, 52, 1234−1243 pubs.acs.org/est Kinetics of Decomposition of Thiocyanate in Natural Aquatic Systems Irina Kurashova,† Itay Halevy,‡ and Alexey Kamyshny, Jr.*,† † Department of Geological and Environmental Sciences, Ben-Gurion University of the Negev, Beer Sheva, Israel 84105 ‡ Department of Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot, Israel 76100 ABSTRACT: Rates of thiocyanate degradation were measured in waters and sediments of marine and limnic systems under various redox conditions, oxic, anoxic (nonsulfidic, nonferruginous, nonmanganous), ferruginous, sulfidic, and manganous, for up to 200-day period at micromolar concentrations of thiocyanate. The decomposition rates in natural aquatic systems were found to be controlled by microbial processes under both oxic and anoxic conditions. The Michaelis−Menten model was applied for description of the decomposition kinetics. The decomposition rate in the sediments was found to be higher than in the water samples. Under oxic conditions, thiocyanate degradation was faster than under anaerobic conditions. In the presence of hydrogen sulfide, the decomposition rate increased compared to anoxic nonsulfidic conditions, whereas in the presence of iron(II) or manganese(II), the rate decreased. Depending on environmental conditions, half-lives of thiocyanate in sediments and water columns were in the ranges of hours to few dozens of days, and from days to years, respectively. Application of kinetic parameters presented in this research allows estimation of rates of thiocyanate cycling and its concentrations in the Archean ocean. ■ INTRODUCTION aquatic systems, as well as to chemical transformations, 24−26 Thiocyanate (NCS−) is formed in various natural and industrial volatilization and adsorption.
    [Show full text]
  • Trinuclear Copper Biocatalytic Center Forms an Active Site of Thiocyanate Dehydrogenase
    Trinuclear copper biocatalytic center forms an active site of thiocyanate dehydrogenase Tamara V. Tikhonovaa,1, Dimitry Y. Sorokina,b,1, Wilfred R. Hagenb, Maria G. Khrenovaa,c, Gerard Muyzerd, Tatiana V. Rakitinae,f, Ivan G. Shabaling, Anton A. Trofimovh, Stanislav I. Tsallagova, and Vladimir O. Popova,f,2 aResearch Centre of Biotechnology, Russian Academy of Sciences, 119071 Moscow, Russia; bDepartment of Biotechnology, Delft University of Technology, Delft, 2629 HZ The Netherlands; cDepartment of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia; dDepartment of Freshwater and Marine Ecology, Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, Amsterdam, 1098 XH The Netherlands; eShemyakin- Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, 117997 Moscow, Russia; fKurchatov Complex NBICS-Technologies, National Research Center “Kurchatov Institute”, 123182 Moscow, Russia; gDepartment of Molecular Physiology and Biological Physics, University of Virginia, Charlottesville, VA 22903; and hEngelhardt Institute of Molecular Biology, Russian Academy of Sciences, 119991 Moscow, Russia Edited by Edward I. Solomon, Stanford University, Stanford, CA, and approved January 27, 2020 (received for review December 29, 2019) Biocatalytic copper centers are generally involved in the activation via initial formation of (NCS)2Cu, comprises multiple stages, and and reduction of dioxygen, with only few exceptions known. gives sulfate as the final sulfur reaction product. Some sulfur- Here we report the discovery and characterization of a pre- oxidizing bacteria (SOB) known to play an important role in viously undescribed copper center that forms the active site of global geochemical cycles can utilize thiocyanate as the sole a copper-containing enzyme thiocyanate dehydrogenase (sug- source of energy and nitrogen.
    [Show full text]
  • United States Patent Office Patented Aug
    3,050,526 United States Patent Office Patented Aug. 2, 1962 2 carbon disulfide or a xanthate, reactions which are known 3,050,526 to give compounds of the structure 3.THOCYANOMETHYL-2-BENZOTHAZOL. NONES AND BENZOXAZOLNONES -NH Chien-Pen Lo, Philadelphia, Pa., asisgn.or to Rohm & 5 R Haas Company, Philadelphia, Pa., a corporation of CY eaware NX/ No Drawing. Fied Alig. 8, 1960, Ser. No. 47,949 which are then reacted with formaldehyde and then a 8 Caims. (C. 260-304) halogenating agent, such as thionyl chloride, phosphorus This invention concerns N-thiocyanomethyl compounds 0 trichloride or tribromide or phosphorus and iodine to of the structure give the halomethyl derivative. When it is desired to have sulfur as X, there may be used an ortho-nitro-chlorobenzene, which is reacted step NCESCN wise with an alkali metal disulfide and monosulfide, fol lowed by ring formation with phosgene or urea. a. Typical methods for preparation of intermediates for forning the necessary halomethyl starting materials may wherein R represents hydrogen, chlorine, bromine, alkyl be summarized as follows: groups, especially lower alkyl groups of one to 8 carbon atoms, alkoxy groups of one to 4 carbon atoms, phenyl, (A) cycloalkyl groups, and Saturated aliphatic monocarboxylic NH --NH acyl groups of 2 to 4 carbon atoms, and X and Y repre R - COCl2 or (NH2)30O - R sent oxygen or sulfur with the proviso that only one of OH Cas O these in a given compound represents sulfur. These No/ compounds are active fungicidal agents for the control of fungus diseases of plants.
    [Show full text]