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    2DNMR

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    2DNMR

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    91 views37 pages

    2DNMR

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    prasad0625

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    Multidimensional NMR Experiments

    Chem 8361/4361: Interpretation of Organic Spectra

    2009 Andrew Harned & Regents of the University of Minnesota

    2D NMR Spectroscopy
    General Information
    More complicated experiments to set up than 1H and 13C Changes in pulses (#, length, angles, mixing times, etc.) Observe effects based on relationship of nuclei
    **Can be homonuclear (same nuclei) (e.g. HH) or heteronuclear (different nuclei) (e.g. HC, HP, etc.)**

    Will only go over the what the experiments tell you and how to interpret, and only for the most common and widely used for solving organic structures
    DEPT, HH COSY, HMQC (HETCOR), HMBC, INADEQUATE (CC COSY)

    There is a whole alphabet soup of other experiments (both 1D and 2D)


    EXSY, TOCSY, HOHAHA, INEPT, WATERGATE, and many more
    http://www.chem.ox.ac.uk/spectroscopy/nmr/acropage.htm

    2D NMR Spectroscopy
    Number of Protons on Carbon
    DEPT (Distortionless Enhancement by Polarisation Transfer
    Used to be known as APT (Attached Proton Test) DEPT is 1H-detected; APT is 13C-detected Tells you how many protons are attached to a particular carbon negative peaks = CH2 positive peaks = CH and CH3 (distinguishable with further processing) missing peaks = carbons w/o protons With a little help from IR and chemical shift of protons, can get a rough idea of molecular weight

    2D NMR Spectroscopy
    Number of Protons on Carbon
    DEPT (Distortionless Enhancement by Polarisation Transfer
    1 = Carbon spectrum 2 = CH2 CH, CH3 3 = CH

    90 pulse 135 pulse

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    Tells you how which protons are coupled to one another Very useful when peaks are overlapping in 1H NMR and you are unable to calculate coupling constants, or when there are a lot of similar coupling constants Cross peaks are coupled to each other

    H C

    H C C

    1 bond HH coupling

    Newer method is DQF (Double Quantum Filtered)-COSY


    same information, but looks cleaner

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    Overlapping protons and a lot of similar coupling constants


    3H 1H 4H 1H 2H 2H 1H 3H 2H

    Exercise 5.10 pp 298

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    Exercise 5.10 pp 301

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    2H 3H 1H 2H 2H 1H 4H 3H

    1H
    pp 301

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    DQF-COSY: Double Quantum Filtered COSY cleans up the spectrum by reducing noncoupled systems (e.g. CH3 singlets)

    CH2

    HO H3C

    CH2 CH3

    Ipsenol

    pp 253

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    DQF-COSY: Double Quantum Filtered COSY cleans up the spectrum by reducing noncoupled systems (e.g. CH3 singlets)

    CH2

    HO H3C

    CH2 CH3

    Ipsenol

    pp 253

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    C6H10O2

    pp 408

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H1H

    COSY (Correlation Spectroscopy)

    O O

    pp 409

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H13C

    COSY

    HETCOR (Heteronuclear Correlation) older experiment; 13C-detected HMQC (Heteronuclear Multiple Quantum Correlation) newer experiment; 1H-detected; largely replaced HETCOR Both give same information, experimentally very different Peaks have one-bond coupling (i.e. attached directly) Compliments DEPT Particularly useful for diastereotopic protons
    H C C C

    1 bond HC coupling

    2D NMR Spectroscopy
    Who is Talking to Who?
    HMQC

    H C C C

    1 bond HC coupling

    2D NMR Spectroscopy
    Who is Talking to Who?
    HMQC

    Diastereotopic Protons
    H C C C

    1 bond HC coupling

    2D NMR Spectroscopy
    Who is Talking to Who?
    HMQC

    Can see into multiplets


    H3C H H3C H H2C CH3 O

    Caryophyllene Oxide

    pp 262

    2D NMR Spectroscopy
    Who is Talking to Who?
    HMQC

    O O

    pp 409

    2D NMR Spectroscopy
    HO Cl

    pp 410

    2D NMR Spectroscopy
    HO Cl

    pp 411

    2D NMR Spectroscopy
    HO Cl

    pp 411

    2D NMR Spectroscopy
    Who is Talking to Who?
    1H13C

    COSY (Long Range)

    COLOC (Correlated spectroscopy for Long range Couplings) older experiment; 13C-detected HMBC (Heteronuclear Multiple Bond Coherence) newer experiment; 1H-detected; completely replaced COLOC Both give same information, experimentally very different Peaks have two- or three-bond coupling Sees through heteroatoms and quaternary carbons Can be very complicated, but is very powerful
    H
    1 1

    H
    1

    H O
    2 3

    O C
    2 3

    C
    2

    C
    3

    2 and 3 bond HC couplings

    2D NMR Spectroscopy
    Who is Talking to Who?
    HMQC

    H C C C

    1 bond HC coupling

    2D NMR Spectroscopy
    Who is Talking to Who?
    HMBC

    H
    1

    C
    2

    C
    3

    2 and 3 bond HC couplings

    2D NMR Spectroscopy
    Who is Talking to Who?

    OH OCH3

    or

    OCH3 OH

    pp 441

    2D NMR Spectroscopy
    Who is Talking to Who?
    OH OCH3

    or
    OH

    OCH3

    pp 442

    2D NMR Spectroscopy
    Who is Talking to Who?
    OH OCH3

    or
    OH

    OCH3

    pp 442

    2D NMR Spectroscopy
    Who is Talking to Who?
    OH OCH3

    or
    OH

    OCH3

    pp 443

    2D NMR Spectroscopy
    Who is Talking to Who?
    OH OCH3

    or
    OH

    OCH3

    pp 443

    2D NMR Spectroscopy
    Who is Talking to Who?
    13C13C

    COSY

    INADEQUATE (Incredible Natural Abundance Double Quantum Transfer Experiment) tells what carbons are attached to each other if you know what type of carbon it is (C, C=O, CH, CH2, CH3, etc.) from DEPT, you can almost write down the entire gross structure by running two NMR experiments

    BUT it is 13C13C coupling


    probability of one 13C is 0.01 two next to each other 0.01x0.01 = 0.0001 (~1 molecule in 10,000) Need lots of sample and instrument time to overcome In our facility: 80% v/v, overnight, 500 MHz = nothing

    O N C C C

    1 bond CC coupling

    2D NMR Spectroscopy
    Who is Talking to Who?
    INADEQUATE

    1 bond CC coupling

    pp 266

    2D NMR Spectroscopy
    Who is Talking to Who?
    INADEQUATE
    Cross peaks show up as doublets = JCC Diagonal is midway between the two doublets
    5 4 1 9 10 3 11 6,7 2 14 15 12

    pp 266

    2D NMR Spectroscopy
    CH C CH CH2 C CH2 CH3,CH3,CH2,CH3

    OH

    pp 297 DEPT on pp 294

    2D NMR Spectroscopy

    pp 434

    2D NMR Spectroscopy

    C,CH

    pp 436

    2D NMR Spectroscopy
    C CH CH C CH2 CH2 CH3 x2 CH3

    Which Isomer?
    Br

    pp 436

    2D NMR Spectroscopy

    Br

    pp 435

    2D NMR Spectroscopy

    Br

    pp 435

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