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Introduction to
SPECTROSCOPY
6
4 : 1 NMR
1 NMR . proton . proton , , , .
6.1 proton: AlcoholAlcohol NMR , hydroxyl hydroxy (CHOH) . geminal , - . Hydroxyl - . , , . hydroxyl proton hydroxyl proton( ) . , alcohol proton NMR . OHb Q ROHb R OHa ROHa R NMR 102103 . alcohol 105 proton proton . alcohol proton 105 . , . , proton ; 2 . NMR , proton hydroxyl proton proton . , NMR proton . , hydroxyl proton alcohol , hydroxyl proton - . 1 , hydroxyl proton ( 2 ,
326
6.1 290 K 200 K methanol NMR .
2 ) , 2 2 0. NMR . . alcohol NMR ( 102103 ), . , 25( 300 K) methanol NMR 2 , proton . 33(240 K ) . OH proton (3J 5 Hz) , methyl proton (3J 5 Hz) . 33(240 K ) NMR hydroxyl proton . 25 33 , . 6.1 290 K 200 K methanol NMR . ethanol ( 6.2), hydroxyl proton methylene proton . hydroxy proton , methylene proton(methyl ) . NMR hydroxyl methylene proton . ( , proton
1
1
1
6 4: 1 NMR
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(ppm)
6.2 ethanol NMR .
) ethanol hydroxyl-methylene - . Hydroxyl , methylene . Hydroxyl methylene 2 (methyl , J ) .
Methylene-hydroxyl 3J(CH2, OH) ca. 5 Hz. Methyl methylene-methyl J(CH3, CH2) ca. 7 Hz . Methylene proton 4 . hydroxyl-methylene methyl-methylene
328
6.3 ethanol NMR . .
. 5 , n 1 . . 6.3 ethanol . methylene proton 2 ( ) .1, 2 ethanol , proton methylene hydroxyl proton .
6.2 D2O A. / Alcohol/ OH 2 , OH NMR . (1) (2) (3) 1 : 1 . 6.4 .
1 . 2 . 1 .
6 4: 1 NMR
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6.4 , 1 : 1 .
hydroxyl 3 . methyl . 2 . Methyl , hydroxyl hydroxyl . CH3COOHa HOHb Q CH3COOHb HOHa , NMR hydroxyl proton. OH . , , hydroxyl . , . Ethanol , ethanol (1%) 2 , . .
B. D2O . . . , phenol, alcohol, amine . phenol , alcohol amine . Basic catalyst RCOOH D2O Q RCOOD DOH ArOH D2O Q ArOD DOH
330
Acidic catalyst ROH D2O Q ROD DOH RNH2 2D2O Q RND2 2DOH 1H NMR . DOH . DOH . DOH , , DOH . NMR D2O . , CDCl3 . NaOD D2O D2O sodium . (D2O ) . Carboxyl , DOH . 2 D2O 2 Na d 2 NaOD D2 RCOOH NaOD Q RCOONa DOH D2O/NaOD ketone, aldehyde, ester . O O RCH2CR 2 NaOD Q RCD2CR 2 NaOH NaOH D2O Q NaOD DOH Amine DCl D2O . Amino proton DOH . RNH2 3 DCl Q RND3Cl 2 HCl HCl D2O Q DCl DOH proton . 1 . methine . (five-line pattern) . Proton- 13C .(4.13)
NMR OH NH proton , proton : NMR , NMR probe . proton . NMR , NMR . H OD 4.55.0 ppm .
6 4: 1 NMR
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6.5 hydroxyl NMR .
C. proton ( ) . . OH . 6.2 hydroxyl . . -, NMR , (coalescence) NMR . 6.5 . alcohol (, CDCl3 CCl4) , NMR - . - . , 3.11C 3.19F .
6.3 : (Tautomerism) (intermolecular) . (dynamic) NMR , . NMR time scale . (tautomer) . tautomerism keto enol tautomerim.
332
, keto enol keto . ketoenol tautomerims . 1,3-Dicarbonyl ketoenol tautomerim . acetylacetone .
1,3-dicarbonyl , enol . enol . 6.6 acetylacetone NMR . Enol OH 15.5 ppm (downfield) , vinyl CH 5.5 ppm . enol CH3 2.0 ppm , keto CH3 2.2 ppm . 3.6 ppm CH3 . , enol . NMR , keto enol NMR time scale . tautomerism valence tautomerism( valence isomerization) . Valence tautomer , tautomer . valence tautomerism . bullvalene .
6 4: 1 NMR
333
6.6 Acetylacetone NMR . Enol tautomer OH .
85 , bullvalene NMR ( ). . 120 . Bullvalene Cope rearrangement bullvalene (rearrangement) .
1 2 cyclopropane , 2 . , , bullvalene 10 . (15) ,
334
, . NMR . NMR (rearrangement) , (isomerization) , (equilibration) . (conformation) , , .
6.4 proton: AmineAlcohol amine proton - proton - . , amino ( ) , amino . (pH 1) amine quaternary ammonium .
6.7 n-Butylamine NMR .
6 4: 1 NMR
335
, amine, proton amine - .
6.8 1-Phenylethylamine NMR .
336
Amine amide proton , proton alkyl - .
n-Butylamine( 6.7) 1-phenylethylamine( 6.8) NHCH . amine . amine amide . 1 (I 1). 1, 0, 1 . - , N H .
geminal vicinal . . . NHCH HOCH proton-proton NH nitrogen-proton . , (1J50 Hz).
6.9 H2O(pH 1)CH3NH3 NMR .
6 4: 1 NMR
337
6.10 Methylammonium chloride NMR : proton.
NH CHNH proton-proton (pH 1) methylamine NMR . methylammonium chloride methylamine HCl . 6.9 . 2.2 ppm ( ) . 6.10 6.11 .
6.5 proton: I 2 . I 2 , (quadrupole) . . 1 1
6.11 Methylammonium chloride NMR : Methyl proton.
338
NMR . ( ). NMR- . (I 0) , . Chlorine, bromine, iodine proton . 1 fluorine(I 2 ) , proton . - , bromine . ( ) . . . 1. . . (NH) (1, 0, 1) 3 .
6.12 Pyrrole NMR . CH proton .
6 4: 1 NMR
339
methylammonium chloride ( 6.9 6.11) . Ammonium, methylammonium tetraalkylammonium 1H14N .3 2. . . 3 , (NH) (zero) . . aniline 1 amine . 3. . (quadrupole broadening) . proton(N H) . 6.12 pyrrole NMR , NH 7.5 8.5 ppm .
6.6 Amide proton . Amide proton NMR NH . proton NH proton . NH ; NH . Amide, amide . , N,N-dimethylformamide(DMF) methyl 2 ( 6.13). 2 CN carbonyl . . , NMR . carbonyl .
. . NMR , NMR 2 methyl ( methyl C carbonyl N ). .
3 borohydride . 1H11B 1H10B .
340
6.13 N,N-Dimethylformamide NMR .
Dimethylformamede , 2 (80100), (120) , (150 ) . , NMR methyl . , methyl proton methyl . . 6.14 N,N-dimethylformamide methyl . 6.15 chloroacetic acid amide NH2 . NH .
6 4: 1 NMR
341
6.14 N,N-dimethylformamide methyl .
, . Amide CN , 2 . amide(RCONHR ), .
6.15 Chloroacetamide NMR .
342
, 2 NH (6.1, 6.2C, 6.4). amide - . 1. 2. 3. NH 2 3 .
6.7 NMR . . . , , FT-NMR . Deuteriochloroform(chloroform-d, CDCl3) . , . . hydrocarbon , (van der Walls London forces) , . (acetone, chloroform dimethyl sulfoxide ), . tetramethylsilane(TMS, ) , . - (solvent-induced shift) proton 0.11 ppm . ( , benzene, pyridine, nitromethane) . TMS . Benzene pyridine ( d) , acetonitrile . . Benzene pyridine , acetonitrile . - . - . CDCl3 benzene-d6 pyridine-d5( 20%)
6 4: 1 NMR
343
. 1 ppm , . benzene .
6.8 : 60-MHz proton . , proton . 60 MHz . 300 400 MHz. NMR , Hertz (3.17 ). . , 3 . proton . 60 MHz, . , proton (HA, HB, HC) Hertz (ppm ) . 300 MHz ( 3.35). 2 300 MHz 1 (5.12A, 5.12F). proton(, hydroxyl amino) . CCl4 CDCl3 NMR benzene , proton . . (chemical shift reagent) 1969 . lanthanide (paramagnetic rare-earth metal) . , proton . ( ) . Europium, erbium, thulium, ytterbium cerium, praseodymium, neodymium, samarium, terbium, holmium . 300 MHz NMR . Lanthanide europium . tris-(dipivalomethanato) europium tris-(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium. Eu(dpm)3, Eu(fod)3 , .
344
lanthanide Eu3 () NMR . aldehyde, ketone, alcohol, thiol, ether, amine .
proton (1) Eu3 proton (2) . , lanthanide- . 1-Hexanol ( 6.16, 6.17)
6.16 1-Hexanol 60-MHz NMR .
6 4: 1 NMR
345
6.17 0.29- Eu(dpm)3 1-haxanol 100-MHz NMR . (: Sanders, J. K. M., and D. H. Wiliams, Chem. Commun., 422 (1970).)
. 6.16 . methyl hydroxyl methylene . proton(OH ) . ( 6.17), methylene . 1 . n 1 . . 6.17, . . , .
6.9 Chiral Chiral chiral R S . racemic chiral (chiral resolving agent) diastereomer , NMR diastereotopic ( ). , enantiomer , diastereomer , . , amine -phenylethylamine R S enantiomer , (S)-()-O-acetylmandelic acid diastereomer .
346
diastereomer amine methyl chiral . R S . methyl diastereomer(diastereotopic), . R S . methyl proton NMR ( ) 1.1 1.2 ppm . Methyl methine(CH) , 6.18 . R S amine . , ()--phenylethylamine , (S)-()--phenylethylamine 50/50 NMR .
6.18 CDCl3 (racemic) -phenylethylamine 50 : 50 300-MHz 1H . Chiral (S)-()-O-acetylmandelic acid .
6 4: 1 NMR
347
6.10 : (double resonance) NMR . - . scan 2 . proton . proton . (6.1) (6.5) , proton - , NMR . , propyl bromide . 60-MHz NMR 6.19A . 6.19B CH2 proton( ) NMR . , CH2 proton . CH2 proton CH2 proton - . CH2 proton 3 methyl proton , . CH2 proton methyl . CH2 proton . 6.19C 6.19D CH2 CH3 proton () .
6.19 Propyl bromide NMR : (A) 60 MHz (B) CH2 proton (C) CH2 proton (D) CH3 proton .
348
. , propyl bromide - . B CH2 proton CH2 proton CH3 . proton CH2 , CH2 proton . C CH2 CH3 proton CH2 A . CH3 proton CH2 proton . , propyl bromide , proton . propyl bromide , . . . Allyl bromide ( 6.20). CH2 proton allyl proton . allylCH2Br proton , alkene (vinyl acetate, 5.17, 5.18) AMX . 6.20 AMX . vinyl J . 10 2DNMR .
6.20 Allyl bromide(CH2 CHCH2Br) NMR ; (a) ; (b) CH2Br proton (: McFarlane, W., Chem. Britain, 5 (1969): 143.)
6 4: 1 NMR
349
6.11 NOE NMR , . , alkene cis trans . Bicyclic , exo endo . . NOE (NOE difference spectroscopy) . Overhauser (4.5) (heteronuclear) (homonuclear) . Overhauser , 13C (broad-band signal) . Overhauser . 3 . . , oscillating . . (dipolar) r6 . r . . , . NOE . (decoupler) . , ( CDCl 3 CHCl3 ). . NOE . . , 2.5 3 . . 6.21 ethyl methacrylate NOE .
350
NMR . vinyl 5.5 6.1 ppm . HE carbonyl HZ . , HZ HE . 1.9 ppm methyl . 1.9 ppm . 5.5 ppm vinyl . 6.1 ppm vinyl . 5.5 ppm HZ . , HE methyl . . 5.5 ppm vinyl 1.9 ppm methyl . . . , 6.1 ppm HE . 5.5 ppm HZ . 1.9 ppm methyl methyl 6.1 ppm . NOE . , alkene bicyclic .
6 4: 1 NMR
351
6.21 Ethyl methacrylate NOE . ( : ethyl methacrylate NMR ; : 1.9 ppm NOE ; : 6.1 ppm NOE ).
352
*1. 6.3 ethanol . Methylene hydroxyl methyl methylene . *2. C5H10O . 1.9 ppm . Hertz . 5.0 5.2 ppm . ? .
6 4: 1 NMR
353
*3. C6H5BrO . 5.6 ppm . 4J 1.6 Hz .
354
*4. 2-Methylphenol . C9H10O2 . 3136, 1648 cm1. 8.16 ppm . 6 . .
*5. . 5.25 ppm . (, ) . 6 . .
6 4: 1 NMR
355
*6. C5H10O 1H NMR . . 2.1 ppm . proton . 4.78 ppm . -13 DEPT-135, DEPT-90 .
Normal Carbon22 ppm 41 60 112 142
DEPT-135Positive Negative Negative Negative No peak
DEPT-90No No No No No peak peak peak peak peak
356
7. C5H10O 1H NMR . 2.1 ppm . 3332 cm1 . -13 DEPT-135, DEPT-90 . .
Normal Carbon11 ppm 18 21 71
DEPT-135Negative No peak Positive Negative
DEPT-90No No No No peak peak peak peak
6 4: 1 NMR
357
8. C9H9ClO3 . 33002400 cm1 , 1714 cm1 . Proton NMR . halogen 3-chlorophenol .
358
*9. C10H15N . Proton NMR . 34203349 cm1 , 1624 cm1 . DCl NMR 3.5 ppm .
6 4: 1 NMR
359
*10. C6H5Br2N . Proton NMR . 34203315 cm1 , 1612 cm1 . -13 DEPT-135, DEPT-90 .
Normal Carbon109 ppm 119 132 142
DEPT-135No peak Positive Positive No peak
DEPT-90No peak Positive Positive No peak
11. 1 amine proton NMR . . ( 6) (, ) .
360
*12. Aniline (chlorination) C6H5NCl2 . . Hertz . . .
6 4: 1 NMR
361
*13. C3H7NO2 amino acid D2O NMR . Amino proton carboxyl proton D2O 4.9 ppm ( ). 7 Hz . .
362
14. C7H9N . proton NMR 7.106.60 ppm . 7 ppm 2 proton . DCl NMR 3.5 ppm . 3400 cm1 751 cm1 (out-of-plane) .
6 4: 1 NMR
363
15. C9H11NO3 amino acid DCl D2O NMR . Amino proton, carboxyl proton, hydroxyl proton D2O 5.1 ppm (4 H) . 3.173.40 ppm .
364
16. C6H10O2 . proton NMR . 6.91 ppm proton 1.47 Hz . 1.83 ppm . -13 DEPT-135, DEPT-90 .
Normal Carbon12 ppm 13 22 127 147 174
DEPT-135Positive Positive Negative No peak Positive No peak
DEPT-90No peak No peak No peak No peak Positive No peak
6 4: 1 NMR
365
366
17. phenacetin(C10H13NO2)(acetaminophen ) . Phenacetin amide . 3.4 8.1 ppm 2 . .
6 4: 1 NMR
367
18. N,N-diethyl-m-toluamide 360 K proton . 290360 K(2787) . 1.2 3.4 ppm .
368
6 4: 1 NMR
369
19. C4H7Cl proton NMR . . 4.52 ppm 1.59 ppm proton .(6.10) 4.52 ppm proton 5.95 ppm 4- . 1.59 ppm 4.52 ppm proton . . 2J, 3J, 4J . 5.95 ppm proton( ) . 4.52 ppm proton . .
370
6 4: 1 NMR
371
20. 11 amine . amine .
*21. Cyclohexane proton NMR . 66.7 . 100 . . *22. cis-1-Bromo-4-tert-butylcyclohexane 4 proton 4.33 ppm . Trans 4 proton 3.63 ppm . 4 proton . 4-bromomethylcyclohexane .
Crews, P., J. Rodriguez, and M. Jaspars, Organic Structure Analysis, Oxford University Press, New York, 1998. Friebolin, H., Basic One- and Two-dimensional NMR Spectroscopy, 2nd ed., VCH Publishers, New York, 1993 Gunther, H., NMR Spectroscopy, 2nd ed., John Wiley and Sons, New York, 1995. Jackman, L. M., and S. Sternhell, Aplications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2nd ed., Pergamon Press, London, 1969. Lambert, J. B., H. F. Shurvell, D. A. Lightner, and R. G. Cooks, Organic Structural Spectroscopy, Prentice Hall, Upper Saddle River, NJ, 1998. Macomber, R. S., NMR Spectroscopy: Essential Theory and Practice, College Outline Series, Harcourt, Brace Jovanovich, New York, 1988. Macomber, R. S., A Complete Introduction to Modern NMR Spectroscopy, John Wiley and Sons, New York, 1997. Pople, J. A., W. C. Schneider, and H. J. Bernstein, High Resolution Nuclear Magnetic Resonance, McGraw-Hill, New York, 1969. Sanders, J. K. M., and B. K. Hunter, Modern NMR spectroscopy-A Guide for Chemists, 2nd ed., Oxford University Press, Oxford, 1993. Silverstein, R. M., F. X. Webster, Spectrometric Identification of Organic Compounds, 6th ed., John Wiley and Sons, New York, 1998. Yoder, C. H., and C. D. Schaeffer, Introduction to Multinuclear NMR, Benjamin-Cummings, Menlo Park, CA, 1987. In addition to these references, also consult textbook references, compilations of spectra, computer programs, and NMR-related Internet addresses cited at the end of Chapter 5.