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NMR
NMR spectroscopy
28
Organic Chemistry
Undergraduate 2
06/30/2010

Additional Organic Chemistry Flashcards

 


 

Cards

Term
# of different H in molecule
Definition
correspond to # if different signals
Term
ratio of # of H atoms of each different type
Definition
determined from ratio of areas under signals
Term
hybridization of C atom that each H is attached to and/or presence of any highly electronegative atoms nearby in the structure 
Definition
determined from position of signal in HNMR spectrum (i.e. chemical shift)
Term
# of neighboring, non-equivalent H atoms
Definition
determined from splitting/multiplicity of each signal
Term

halomethanes (CH3-)

(i.e. CH3F)

Definition

*as electronegativity of halogen increases (F=most electronegative), electron density at H atom decreases

 

-H will be more deshielded-->chemical shift=greater

 

-Exs: CH3F=4.26 vs CH3Cl=3.05

Term
each different H atom in molecule gives rise to different signal
Definition
happens because magnetic field at each different H atom=unique
Term
position of signal in HNMR=characteristic of hybridization of C atom that H is attached to and/or presence of highly electronegative atoms nearby in structure
Definition
these factors vary the induced magnetic field
Term
greater the # of H atoms of each different type, the greater the amount of energy absorbed for that excitation  
Definition
intensity of each signal=proportional to # of H atoms of each type
Term
info from NMR
Definition

*# of signals

*integration (measured by area under peaks)

*chemical shift

*splitting pattern (multiplicity) n+ 1

*coupling constants

Term
shielding
Definition

-electrons shield atom's nucleus

-as shielding increases, magnetic field at nucleus decreases, so energy required to bring nucleus into resonance (flip spin) also decreases

-nucleus that's more shielded comes into resonance at lower frequencies

Term
upfield/downfield
Definition

-upfield: to right-->shielded

-downfield: to left-->deshielded

Term
shielding depends on 3 factors
Definition

1. electronegativity of nearby atoms

2. hybridization of adjacent atoms

3. magnetic induction w/in adjacent pi bonds

-increased shielding means upfield

Term
n + 1 rule
Definition

-signal splitting tells about types of Hs on neighboring Cs

-degree of signal splitting determined by n+1

*if H has n Hs nonequivalent to it but equivalent among selves on same/adjacent C, it's HNMR signal split into n+1 peaks

Term
geminal coupling
Definition

-nonequivalent H's on the SAME carbon will couple to each other and cause splitting

-can be nonequivalent H's when there's restricted bond rotation (i.e. in alkenes or cyclic structures)

-geminal coupling constants=small-->0-5 Hz

Term
alkenes: trans coupling vs cis coupling
Definition

-larger coupling constants for trans-->11-18 Hz

-smaller for cis-->5-10 Hz

-geminal=smallest-->0-5 Hz

Term
determining # of signals from a structure
Definition
count # of nonequivalent Cs/Hs
Term
chemical shifts depend on:
Definition

-electronegativity of nearby atoms

-magnetic induction w/in adjacent pi bond

Term
chemical shift
Definition
slides have tables
Term
vicinal
Definition
w/in 3 bonds
Term
coupling constants
Definition

-distance btwn peaks in a split signal

value=measure of magnetic interaction of nuclei whose spins are coupled

Term
alkanes
Definition

HNMR--> .8-1.7

CNMR-->10-60

Term
alkenes
Definition

HNMR-->4.6-5.7

CNMR-->100-160

 

Term
alcohols
Definition
OH groups don't have very distinctive chemical shifts
Term
ethers
Definition

distinctive in HNMR spectrum

3.3-4.0 of Hs on C attached to ether oxygen

Term
aldehydes and ketones
Definition

-aldehyde Hs at 9.5-10.1

-alpha Hs of aldehydes amd ketones ta 2.2-2.6

-CNMR-->carbonyl Cs at 180-215

 

Term
carboxylic acids
Definition

HNMR-->carboxyl Hs at 10-13

CNMR-->carboxyl Cs at 160-180

Term
amines
Definition
HNMR-->.5-5.0; not very distinctive
Term
steps for NMR (MSICS)
Definition

1. look at molecular formula: determine SODAR

2. # of signals: to determine # of diff. types of H/C

3. Integration: to determine # of Hs in each signal

4. Pattern of chemical shift: to determine functional groups

5. Splitting patterns: to determine # of nearest nonequivalent Hs

6. Structural formula: make possible structures from previous info and confirm by checking w/ spectra

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