Promieniowanie mikrofalowe w ... - Dydaktyka …do.chem.uni.wroc.pl/system/files/PSpec_2015_AKL_mikrofale.pdfPromieniowanie mikrofalowe w chemii organicznej Alicja Kluczyk 18 stycznia

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  • 2016-01-18

    1

    Promieniowanie mikrofalowe w chemii organicznej

    Alicja Kluczyk

    18 stycznia 2016

    Kuchenka mikrofalowa

    naczynia

    potrawy

    czas

    moc

    ilo materiau

    czego nie naley wkada do mikrofalwki?

    https://www.youtube.com/watch?v=t0Gw50o7iuA

    https://www.youtube.com/watch?v=9F1KUp4G1uo

    Rys historyczny

    nieprzewidziane konsekwencje zastosowania

    radaru czyli co Percy LeBaron Spencer nosi

    w kieszeni

    baton orzechowy

    popcorn

    jajko

    Percy LeBaron Spencer

    http://www.gallawa.com/microtech/history.html

    Kuchenny rys historyczny

    1947 RADARANGE (2 000-3 000 $)

    1952-55 model domowy (1 295 $) 2450 MHz

    Panasonic NE1846 6 999 z

    AEG Micromat Combi 3880 E-M 3 300 z 140 z

    https://www.youtube.com/watch?v=t0Gw50o7iuAhttps://www.youtube.com/watch?v=t0Gw50o7iuAhttps://www.youtube.com/watch?v=t0Gw50o7iuAhttp://en.wikipedia.org/wiki/File:Magnetron_section_transverse_to_axis.JPG

  • 2016-01-18

    2

    B. L. Hayes, Microwave synthesis, CEM Publishing, 2002

    Parametry

    staa dielektryczna '

    strata dielektryczna

    przeksztacanie energii mikrofal w ciepo

    tan (tan = / )

  • 2016-01-18

    3

    Jak uzyska wysok temperatur dla niskowrzcego rozpuszczalnika?

    Zastosowania naukowe

    microwave synthesis

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    1975

    2013: 2 518 prac w Web of Science

    2014: 2 614

    2015: 2 538

    Mineralizatory i ekstraktory Syntezator mikrofalowy CEM Discover

    http://cem.com/page153.htmlhttp://cem.com/page36.htmlhttp://cem.com/page37.htmlhttp://cem.com/page38.htmlhttp://cem.com/page39.html

  • 2016-01-18

    4

    http://www.anton-paar.com/001/en/60/557 http://www.anton-paar.com/001/en/60/557

    Microwave SPPS System

    Mikrofale i .

    fotochemia

    synteza organiczna (warunki homogeniczne)

    synteza organiczna na noniku staym * **

    chemia zwizkw heterocyklicznych

    katalizatory metale przejciowe

    cykloaddycja

    odczynnki na noniku

    reaktory cinieniowe

    radiochemia

    kataliza homogeniczna

    efekty nietermiczne *

    katalizatory przeniesienia fazowego

    Reakcje wspomagane

    MAOS

    Microwave-Assisted Organic Synthesis

    MEC

    Microwave-Enhanced Chemistry

    MORE

    Microwave-organic Reaction Enhancement

  • 2016-01-18

    5

    Proste przykady

    Green chemistry

  • 2016-01-18

    6

    Title: Microwave-assisted stereoselective alpha-2-deoxyglycosylation of hex-1-en-3-uloses Author(s): Lin HC, Wu HH, Lin ZP, et al. Source: TETRAHEDRON LETTERS Volume: 50 Issue: 52 Pages: 7327-7329 Published: DEC 30 2009

    Title: Microwave-assisted McMurry polymerization utilizing low-valent titanium for the synthesis of poly 2,6-[1,5-bis(dodecyloxy)naphthylene vinylene] (PNV) Author(s): Thomas H, Stuhr-Hansen N, Westerlund F, et al. Source: TETRAHEDRON LETTERS Volume: 50 Issue: 52 Pages: 7374-7378 Published: DEC 30 2009

    Title: Microwave-Assisted, Rapid, Solvent-Free Aza-Michael Reaction by Perchloric Acid Impregnated on Silica Gel Author(s): Singh SP, Kumar TV, Chandrasekharam M, et al. Source: SYNTHETIC COMMUNICATIONS Volume: 39 Issue: 22 Pages: 3982-3989 Published: 2009

    Title: Novel One-Pot Synthesis of 3-Phenylnaphtho[2,3-b]furan and 3-Phenylbenzofurans Under Microwave Irradiation and Solvent-Free Conditions Author(s): Wang ZX, Gu JZ, Jing HW, et al. Source: SYNTHETIC COMMUNICATIONS Volume: 39 Issue: 22 Pages: 4079-4087 Published: 2009

    Title: Synthesis and characterization of Eu-doped hydroxyapatite through a microwave assisted microemulsion process Author(s): Yang C, Yang PP, Wang WX, et al. Source: SOLID STATE SCIENCES Volume: 11 Issue: 11 Pages: 1923-1928 Published: NOV 2009

    Title: Synthesis, Spectral and Biological Evaluation of Some Mesoporphyrinic Zn(II) Complexes Author(s): Boscencu R, Socoteanu R, Ilie M, et al. Source: REVISTA DE CHIMIE Volume: 60 Issue: 10 Pages: 1006-1011 Published: OCT 2009

    Title: Synthesis and Antimicrobial Activity of New Aromatic Esters of Potential Interest in Supramolecular Chemistry Author(s): Balan AM, Zbancioc G, Bentea E, et al. Source: REVISTA DE CHIMIE Volume: 60 Issue: 10 Pages: 1021-1024 Published: OCT 2009

    Title: Synthesis of Novel Flower-Like Zn(OH)F via a Microwave-Assisted Ionic Liquid Route and Transformation into Nanoporous ZnO by Heat Treatment Author(s): Song JK, Zheng MB, Yang ZJ, et al. Source: NANOSCALE RESEARCH LETTERS Volume: 4 Issue: 12 Pages: 1512-1516 Published: DEC 2009

    Title: Microwave-assisted solid-phase peptide synthesis at 60 degrees C: alternative conditions with low enantiomerization Author(s): Loffredo C, Assuncao NA, Gerhardt J, et al. Source: JOURNAL OF PEPTIDE SCIENCE Volume: 15 Issue: 12 Pages: 808-817 Published: DEC 2009

    Title: Microwave-assisted synthesis of ZnO micro-javelins Author(s): Padmanabhan SC, Ledwith D, Pillai SC, et al. Source: JOURNAL OF MATERIALS CHEMISTRY Volume: 19 Issue: 48 Pages: 9250-9259 Published: 2009

    brak

    rozpuszczalnika

    selektywno

    ciecze jonowe

    nonik stay **

    nonik stay *

    1.

    Microwave-Assisted Bleaching of Wool Fabrics

    By: Abou El-Kheir, Amira; Haggag, Karima; Mowafi, Salwa I.; et al.

    JOURNAL OF NATURAL FIBERS Volume: 12 Issue: 2 Pages: 97-107 Published: MAR 4 2015

    2.

    Microwave-assisted synthesis of graphene-Ni composites with enhanced microwave absorption properties in Ku-band

    By: Zhu, Zetao; Sun, Xin; Li, Guoxian; et al.

    JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS Volume: 377 Pages: 95-103 Published: MAR 1 2015

    3.

    Single-crystalline AgIn(MoO4)(2) nanosheets grafted Ag/AgBr composites with enhanced plasmonic photocatalytic activity for

    degradation of tetracycline under visible light

    By: Yan, Xu; Wang, Xiyou; Gu, Wei; et al.

    APPLIED CATALYSIS B-ENVIRONMENTAL Volume: 164 Pages: 297-304 Published: MAR 2015

    4.

    Inhibition of photocorrosion and photoactivity enhancement for ZnO via specific hollow ZnO core/ZnS shell structure

    By: Yu, Linhui; Chen, Wei; Li, Danzhen; et al.

    APPLIED CATALYSIS B-ENVIRONMENTAL Volume: 164 Pages: 453-461 Published: MAR 2015

    5.

    Preparation, characterisation and physicochemical properties of the phosphate modified peanut protein obtained from

    Arachin Conarachin L.

    By: Yu, Lina; Yang, Weiqiang; Sun, Jie; et al.

    FOOD CHEMISTRY Volume: 170 Pages: 169-179 Published: MAR 1 2015

    6.

    Optimisation and validation of the microwave-assisted extraction of phenolic compounds from rice grains

    By: Setyaningsih, W.; Saputro, I. E.; Palma, M.; et al.

    FOOD CHEMISTRY Volume: 169 Pages: 141-149 Published: FEB 15 2015

    7.

    Negative pressure cavitation-microwave assisted preparation of extract of Pyrola incarnata Fisch. rich in hyperin, 2 '-O-

    galloylhyperin and chimaphilin and evaluation of its antioxidant activity

    By: Yao, Xiao-Hui; Zhang, Dong-Yang; Luo, Meng; et al.

    FOOD CHEMISTRY Volume: 169 Pages: 270-276 Published: FEB 15 2015

    http://www.uni-graz.at/~kappeco/index.htm

    Enhanced Deprotection, Coupling, and Cleavage Reactions

    Galanin Synthesis

    Reaction Reagents Time Max Temp.

    (C)

    Deprotection 20% Piperidine / DMF 3 min 21=A, 75=B

    Coupling HBTU/HOBt/DIEA 0.9/1/1 ,

    x10 excess

    4 min 21=A, 75=B

    Cleavage Reagent K

    18 min 38=A and B

    GWTLNSAGYLLGPQQFFGLM-NH2 Conditions

    Scale: 0.10mmol w/ MBHA Rink Amide Resin, 0.59meq/g. (Novabiochem)

    A= Conventional

    B= Microwave

    GWTLNSAGYLLGPQQFFGLM-NH2

    Conventional

    (Purity = < 10 %)

    Microwave

    (Purity = 84.8%)

    Efekty nietermiczne?

    czy rnice w:

    szybkoci

    wydajnoci

    selektywnoci

    to tylko wynik szybkiego, rwnomiernego

    ogrzania reagentw?

    czy w ogle s rnice?

    http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=1http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=1http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=1http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=2http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=3http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=3http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=3http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=3http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=4http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=5http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=5http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=6http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=6http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=6http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=5&SID=P2mNHdyddMuthUxwJxL&page=1&doc=7

  • 2016-01-18

    7

    ania

    olejowa

    reaktor

    mikrofalowy

    Img_8960.jpg

    Natalia Wisowska, 2006.

    Termostat Obserwacja Palladium Catalyzed Aminocarbonylation of Aryl

    Halides

    Carbonylation reactions those which incorporate CO

    into a molecule often pose experimental challenges

    due to the difficulties which accompany the use of

    carbon monoxide gas at elevated pressure. In situ

    generation of CO gas from reaction of potassium tert-

    butoxide and dimethylformamide provides a safe and

    convenient route for carbonylation reactions. The

    microwave assisted, palladium catalyzed

    aminocarbonylation of aryl halides with in situ

    generated carbon monoxide has been reported.2 With

    the Discover SP camera, both color change and

    continued generation of carbon monoxide gas can be

    observed throughout the reaction, assisting with rapid

    reaction optimization.

    1) Leadbeater, N. E.; McGowan, C. C. Clean, Fast Organic Chemistry; CEM Publishing, 2006.

    (2) Wan, Y.; Alterman, M.; Larhed, M.; Hallberg, A. J. Org. Chem. 2002, 67, 6232.

  • 2016-01-18

    8

    Praktyka

    dobr rozpuszczalnika

    monitorowanie reakcji

    dobr reagentw

    wydzielanie produktw (SP)

    dodatkowe efekty?