Introduction to

SPECTROSCOPY

5

3 : 3 4 NMR . . , 2 - . Enantiotopic diastereotopic . 6 (alcohol, acid, amine amide) NMR , tautomer NMR . (, ) 6 .

5.1 : 3 3.17 3.18 . (Hz) J . NMR . J . (homonuclear coupling) . 3 (three-bond coupling) , n 1 . . (heteronuclear coupling) , -13 (one bond heteronuclear coupling) . 2 (bond) . , . , . J , (bond) . , . -13 (CH) 156 Hz .1 13

J( C1H)156 Hz

236

5.1 J .

HCCH .3 1

J( H1H)8 Hz

. , J1,3 1 3 . JCH JHH . J1, J2, J3 . J . , . 5.1 , J , . , . , . J .

5.2 : , . . Dirac . , . Dirac , , , . , ( ) ( ) ( ), .

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, . , . , (1J, 3J, ) , .

A. (One-Bond Coupling, 1J) - , (one-bond coupling) . A B . Pauli orbital . Dirac . 13CH , 13C ( ) ( ) .

13CH ( 1H1H, 31PH ) . . - ( ) J . J . 13C19F ( 5.1). 13CH 1J s- . 5.1 . ethane, ethene, ethyne 13CH .1J CH

(500 Hz)

(

1 n1

)

for hybridization type spn

( 5.1)

5.113

(1J)110270 Hz sp3 115125 Hz (ethane 125 Hz) sp2 150170 Hz (ethene 156 Hz) sp 240270 Hz (ethyne 249 Hz)

C1H

13

C19F

165 to 370 Hz 4856 Hz 2030 Hz 190700 Hz

13C31P 13

CD

31P1H

Dirac - , - . , 13C H . Proton- 13C NMR 13C (2 ) 13C 13C NMR (4.3 4.3). 5.2

238

5.2 CH

: (a) ( ) (b) ( ).

13C

. 5.2 13CH . 1 ( 2 ) , ( ) , . . . 5.2 . . ( ) , , 1 ( ) . 13C ( 2 ) . proton- NMR methine (13C1H).

B. (Two-Bond

Coupling, 2J)

NMR . 2 geminal (geminal coupling)( gemine ) .

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5.2

(2J)

a

Absolute value.

J , 2 2 . 5.2 . , ( 5.2). HCH ( ) . Geminal (2J) - . 5.2 5.2 A Dirac . 5.3 . ( ) 2 . , , . 5.3 . Geminal HCH . 5.4

2

5.3 Geminal .

240

5.4 HCH 2JHCH, geminal .

, CH 2J . 2J geminal . 5.3 2 . 5.4 , . geminal HCH . HCH .

5.3 alkene . 2 J . , cyclohexane(2J 13) cyclopropane(2J 4) . CCC (p ) HCH (s ), geminal . alkene . , geminal HCH (- ) , geminal proton (5.3).

5.3 2JHH

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n 1 , proton . - ? . geminal . bicyclo[2.1.1]hexane bicyclic .

Geminal . - , (I 1) geminal . ( ) HCD HCH . , HCH HCD (JHH 6.55 JHD)1. - 5.3 .

C. (Three-Bond

Coupling, 3J)

, CH CH .

HCCH vicinal (vicinal couplings) . ( vicinus . Vicinal ) (three-bond coupling) 3J . 3.13 3.17,

1 6.55 H D : H/D 6.55

242

n 1 - . , . CC CH , . , CH . 2 CH .

5.5 2 proton . (zero) (12C). . , HCCH . 3 . vicinal CH (dihedral angle) .

5.5 2 CH .

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proton 2 .

Vicinal (3JHH) , Hertz . CH . 5.6 Newmann . HA HB 0 180 90 . C H - 0 , CH . 90 . 180 , .

Martin Karplus 3JHH . 5.7 . Karplus .3J A B HH

A7

cos C cos 2 B 1 C5

( 5.2)

5.6 (dihedral angle) .

244

5.7 Karplus 3J .

- A, B, C . . 5.7 . 5.2 Karplus ( 5.7) Karplus . ) Karplus Dirac . CH ( 90 , . ), 3JHH 0. , ( 0 3J max). ), ( 180 ( HH 5.7 . ( 5.8) RCC, 1 2, X .

5.8

3

JHH .

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, 2 CH 5.7 . (conformationally) cyclohexane . tert-butyl (equatorial) , . 2 (axial) (Jaa) 1014 Hz( 180 , (Jae) 45 Hz( ) ). 60 . (Jee) 45 Hz( 60 )

Cyclopropane . Jcis( 0 Jtrans( 120 ) ) .

5.4

(3Jxy)68 5 Hz 520 Hz 3 to 20 13 Hz 515 Hz Hz HC CH HC 19F C19FC C19F

HCCH13CCCH 19FCCH 19FCC19F 31PCCH 31POCH

cis trans cis trans cis trans

615 Hz 11-18 Hz 18 Hz 40 Hz 3040 Hz 120 Hz

246

5.4 . Alkene trans cis . 5.5 alkene . HCH (3JHH)

D. (Long-Range Coupling, 4J-nJ)3 allylic (5.7) (5.11), bicyclic (5.13 ) .

5.5

alkene 3JHH (Hz)

5.3 3 3.8 . 2 (chemically equivalent) . .

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1 acetone 2 methyl . 2 methyl 13C NMR . CC 6 1H NMR . 2 1,2-dichloroethane, 2 methylene(CH2) . 2 vicinal( threebond) (3J) , 4 1H NMR - . 3 4 . 3 , trans vinyl - ( 2 ). 4 trans-2,3dimethylcyclopropanone 2 () 5 cis-2,3-dimethylcyclopropanone () . , ( ) NMR . (magnetically equivalent) . . . . 1. (isochronous) . . 2. . . , , , NMR ( ) . , - . . Chloromethane, methyl , 3 (CCl ) 3 ( CCl ) , , . methyl CCl . , 3 . Chloromethane 3 NMR (isochronous). ,

248

3 ( ) .

, . 3-pentanone 2 ethyl . (3 CH2) (2 CH3) . 2 ethyl . , 2 methyl 2 methylene . Methyl methylene (3J) ( ), . .

para X Y para- benzene . . 1H (2 ) . , . Ha Ha Hb Hb . Ha Ha Hb Hb () . . , Ha Hb (, 3J) Ha Hb (, 5J) . Hb Ha Ha , Ha Ha (5.11B). Ha , Hb Hb . ? proton : proton . n1 1 (5.4). 2 . 2 . 1,11 difluoroethene. fluorine (19F, 2 ). Ha Hb Fa

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(3JHF) , . cis(3Jcis) trans(3Jtrans). 5.4 alkene cis trans . 3Jtrans . , . 2 fluorine , .

1-chloropropane . (C1, C2, C3 ) , . , , , . , . C2 Hb Hb C1 C3 . ( ) . Jab Jab . .

5.4 : n 1 proton ( ) n 1 . proton ( ), n 1 . n + 1 (1,1,2-trichloroethane) (styrene oxide) . 3 3.13 3.25 1,1,2-trichloroethane . CH2CH 3 - 2 methylene proton(CH2) . CC methylene proton . , methylene proton , ( ) . , 2 proton methine(CH) J . , geminal (splitting) . n 1 CH2 proton ( ), CH proton (2 ) . 5.9a . 5.10 styrene oxide 1H . proton HA HB .

250

5.9 .

. HA phenyl , HB . HA 2.75 ppm HB 3.09 ppm , geminal . proton HC (HC = 3.81 ppm) HA(trans) HB(cis) . HA HB , HC HB HA (3JAC 3JBC), n 1 , styrene oxide . , . . 5.9b . Styrene oxide (graphical analyses) (tree diagrams) ( 5.11). HC . , HB HC (3JBC). HA (3JAC). . HA HB . , . 1 mm2 . 3J (cis) 3J (trans) . BC AC cis proton trans (5.2C). HC 3.81 ppm 4 ( ) . HA HB 2.75 ppm, 3.09 ppm 4 ( ) . 5.11 . HA HB geminal (2JAB) . . , . . . . , 3JBC(cis) HC , HB . 3JAC(trans) HC HA

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5.10 Styrene oxide 1H NMR .

. 2JAB(geminal) HA HB . , . 7.28 ppm NMR phenyl proton . proton , 3 . . .

5.11 Styrene oxide .

252

. 5.10 . 1 n 1 : (1) 2 (, , 4.13 ) , (2) proton (nonequivalence) , (3) ( ) proton , , . 5.10 .

5.5 1 . . 5.10 . 300 MHz .

A. : J (

)

J . Hz . 3 3.17 . ppm Hz . 5.6 . 1 ppm(in Hertz) (Hz) 1,000,000 n MHz 1 ppm n Hz . ppm . ppm Hz . FT-NMR ppm Hz ppm Hz . 5.12 ppm Hz 300 MHz FT-NMR . ppm , Hz . Hz . 5.6 1 ppm . Hz 6.889, 6.858, 6.852, 6.895, 6.871 6.820. Spectrometer Hertz Equivalent Frequency of 1 ppm . , 60 MHz 60 Hz 100 MHz 100 Hz 300 MHz 300 Hz 500 MHz 500 Hz .

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. . , . . . . J . .( .) J 0.2 0.5 Hz . 5.12 6.864 Hz 6.9 Hz .

B. : J , J . 5.13 . , J1 . 1, 2 5.12 ppm Hz 300 MHz 3, 4 . .() . , 1 3 2 4 J1 . (, ) . . . , . 5.14 . 2 5 J1 . 5.15 , . .( )

5.6 Alkene proton NMR sp3 proton . .

254

5.13 (dd) .

5.14 (dt) .

5.15 , (ddd) .

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. proton(vinyl proton) 6 2 . proton . n 1 . alkene, HA, HB, HC 3 proton .

, proton , .

trans proton , 3J 16 Hz . Cis 8 Hz . methylene proton geminal . alkene 1H NMR trans-cinnamic acid 5.16 . Phenyl proton 7.4 7.6 ppm , acid proton 13.21 ppm . HA HC 2 vinyl proton phenyl 7.83 ppm 6.46 ppm . Phenyl proton HC . 5.16 300-MHz 3JAC . 16 Hz( trans proton-proton ). cis . C ( ) cis trans C . vinyl . cis trans-stilbene . vinyl proton HA HB .

256

5.16 trans-Cinnamic acid 1H NMR .

5.17 Vinyl acetate NMR .

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5.18 Vinyl acetate .

Vinyl acetate 3 NMR . proton proton . 5.17 styrene oxide ( 5.10) . (4 ) . 5.18 vinyl . 3J BC(trans) 3 JAC(cis) 2JAB(geminal) ( vinyl ). . alkene n 1 .

5.7 Alkene : Allyl Alkene cis trans vicinal , methylene proton , geminal . 5.19 . 3J trans 2 CH cis . Geminal HCH 120 5.4 . , alkene - proton proton .

258

5.19 Alkene .

(4J) allyl (allylic coupling) . ( 5.20). allyl CH 4J 0 Hz. allyl CH C C () 4J 3 Hz. 5.20 . Allyl . 5.21 crotonic acid NMR . . proton 12.2 ppm . Allylic alkene 3Jtrans . 1.92 ppm , 5.86 ppm 7.10 ppm . CHB allyl (4J) , HACC , - . (4J 0) , HA allylic . allyl .( 5.20)

5.8 : Allyl 4-allyloxyanisole 300-MHz FT-NMR . 5.22 .

Allyl a-d . Methoxy ( , , 3.78 ppm) para- benzene (, 6.84 ppm) . para-

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5.20 Allyl .

5.21 Crotonic acid NMR .

260

5.22 4-Allyloxyanisole 300-MHz FT-NMR .

benzene 5.11B . allyl . Allyl . .

a allyl OCH2 (4.48 ppm) 2H . . anisole methoxy(3.77 ppm) . OCH2 d . trans- c 3Jcd , , cis- b 3Jbd . OCH2 3Jad . .

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vinyl cis- trans- . c b d trans 3Jcd b cis 3J . c bd b . 1H . , . (subpeak) Hz . , .

. a OCH2 . 5.23a . (dt) . ( 5.22) , (ddd) . OCH2 d (3Jad), b (4Jab), c (4Jac) . b c n 1 . b c OCH2 . 4Jab 4Jab . . 5.23b . 1.47 Hz 5.15 Hz . 5.15 Hz vicinal (3Jad) 1.47 Hz cis trans allyl (4Jab 4 Jac) . 5.23c . , . . .

5.23 Allyloxyanisole. (a) Ha . (b) (Hz) . (c) .

262

b . ( 5.24a) . cis 3Jbd . geminal 2Jbc , allyl geminal 4Jab .( ) , (ddt). Ha . 5.24c 2Jbc 4Jab . , ( ) , (5.6 5.7 geminal allyl ). 5.24b J (1.47 10.3 ppm) . 5.24c , . c , b . 5.25 . b . c 3Jcd-trans 3J -cis( b ) . bd allyl .3

Jcd-trans 17.3 Hz 3 Jbd-cis 10.3 Hz 3 Jad-vic 5.5Hz 2 Jbc-gem 1.47 Hz 4 Jab-allyl 1.47 Hz 4 Jac-allyl 1.47 Hz

d . . ( ) .

5.24 Allyloxyanisole. (a) Hb . (b) (Hz) .(c) .

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5.25 Allyloxyanisole. (a) Hc . (b) (Hz) .(c) .

NMR . . 5.24b 1.47 Hz 1.11 Hz . (5.10), . .

d J 5.26a d Hz 5.26b . , . , . 5.26c J . , (ddt) . . .

. , ( ) . , . , . , . . .

264

5.26 Allyloxyanisole. (a) Hd . (b) (Hz) . (c) .

5.9 n + 1 ? , n 1 proton vicinal (3J) (2 ) .

. A C proton B proton . A C 4 proton n 1 . 3JAB 3JBC . 5.27 . A proton B proton (3JAB) 1:2:1 . C proton (3JBC, 1:2:1).

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4 methylene .

5.27

5.28 3JAB 3JBC .

. . ( 5.27). Pascal (3.16) . n 1 . 3JAB 3JBC . , (Hertz NMR .). 3JAB 3JBC A, B, C proton . , (shoulder) (dip) . 3JAB 3JBC 5 . X, Y XCH2CH2CH2Y . 5.28 . methylene . propylbenzene methylene proton .

, (shoulder) . .

5.10

2 :

A. 1 2 n 1 ( )

266

1 (first-order spectrum) . n 1 , , . . 2 (second-order spectrum) . 2 proton J(Hz) . , 2 . , 1 (first-order coupling) .

v/J , v J . Hertz . v/J (10), 1 (first-order splitting) . v/J 1 , 2 . v/J 1 , , v/J 2 , .

B. NMR . proton A, B, C . proton 2 , A2 B3 . proton A, B, C . proton : X, Y, Z A, B, C. 2 proton CHACHX HA HX , 1 . AX . 2 2 proton AB . 2 proton A2 . 2 proton AA . 3 proton , (M) AMX . ABC 3 proton . .

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5.29 1 (n1 ) (v ).

C. A2, AB AX 2 proton HA, HB . n 1 , 1H NMR . (v) proton A B (3JAB) , . 5.29 . 5.30 2 proton HAHB , HA HB v/J , . 3JAB 7

5.30 v/J proton 2 HAHB .

268

Hz . H A HB( HA HB proton ) , v/J 0/J 0 . proton . , (v/J 0) n 1 1 (v/J 15) , 5.31 2 proton . , , . . . , HA HB 1 , 2 HA HB

5.32 v/J proton (CHCH2) .

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. A B . (Hz) . (14) (23 (AB) 4555555555555) 1 (Hz , TMS ) 2, 3, 4 , , 1 ( 5.31). HA HB 5.31 2 (A B) .

D. AB2... AX2 A2B2... A2X2 2 , 5.32 5.33 (CHCH2 CH2CH2) 1H . 1 (v/J 10), (v/J 0 ) 2 . 5.32 5.33 AB2(v/J 10) AX2(v/J 10), A2B2(v/J 10) A2X2(v/J 10).

5.33 v/J proton (CH2CH2) .

270

5.34 Diethyl succinate 1H NMR (60MHz).

, . 5.34 5.37 A2B2 60 MHz 1H NMR . 5.33 .

5.35 Phenylethyl acetate 1H NMR (60MHz).

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1000 500 250 100 50

800 400 200 80 40

600 300 150 60 30

400 200 100 40 20

300 100 50 20 10

0 CPS 0 CPS 0 0 0

(a) (b)

O

(b) (a) CH2 CH2

Cl

A 2B

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0 PPM

5.36 -Chlorophenetole 1H NMR (60MHz).

E. 2 . proton . , NMR . NMR (

5.37 2-Chloroethanol 1H NMR (60MHz).

272

) (simulation) PC workstation . . ( ) . .

F. 2 2 proton 300 MHz . 3.17 3.18 .(3.35). v( ) , J( ) . v/J 2 . 1 . , 5.37 60-MHz 2-chloroethanol 1H . 2 A2B2 . 5.38 300 MHz 1H , 2 2 . 500 MHz 2 n 1 1 A2X2 .

G. 1 . 5.33 A2B2... A2X2 . v/J 2 ? v/J6 v/J10

5.38 2-Chloroethanol 300 MHz proton : 1 A2X2 .

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A2X2 . 14 6 . v/J 6 10 , . , . , . , . 5.30 v/J 3, 6, 15 AB 1 . v/J 36 ( 5.31 ). 2 , . 1 (deceptively simple spectrum) . 1 n 1 . 2 , . ? 1 . 1 . . . , . , n 1 . (error) .

H. , . Styrene oxide( 5.10) vinyl acetate( 5.17) AMX . M A X . 3 (A, M, X) . Trans-cinnamic acid( 5.16) AX .

5.11

:

Phenyl , NMR . , benzene(benzenoid) proton 7.3 ppm . (electron-withdrawing) (, nitro, cyano, carboxyl, carbonyl) , proton , (electron-donating) (, methoxy, amino) . 5.7 para- benzene . Para-

274

5.7

Para benzene 1H

. proton NMR () . benzene , . 6 6.3 . , benzene . 60 MHz 300 MHz . benzene 60 MHz 2 300 MHz 1 .

A. Alkylbenzene benzene 60 MHz proton . alkyl benzene . ortho, meta, para proton , . , . proton . Alkylbenzene NMR . 5.39a ethylbenzene 60 MHz 1H . 5.39b ethylbenzene 300-MHz . 300 MHz ( 5.37 ), 60 MHz proton . Ortho para proton meta proton . 2.

, proton 60 MHz . Methoxy ortho para ( ) proton meta . .

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5.39 Ethylbenzene 1H NMR (a) 60 MHz (b) 300 MHz.

60 MHz, 2 anisole(methoxybenzene) , proton 2 ortho/para proton meta proton . Anisole 60 MHz-NMR o, p proton(3 proton ) meta proton(2 proton ) , ( 5.40), aniline(aminobenzene) amino 3:2 . Anisole 300-MHz ortho/para ( ) meta ( ) . , v(Hertz) , 2 , 300 MHz . 1 , proton (5.3) . Anisole AA BB C .

- Carbonyl nitro , ( ) . ortho para ortho/para

276

5.40 Anisole 1H NMR (a) 60 MHz (b) 300 MHz.

anisole (3:2 : ) . . nitrobenzene benzaldehyde NMR . ortho proton meta para proton . carbonyl benzene .( 5.41) , proton 2 5 . 4 1 Benzaldehyde . Ortho proton meta/para proton ortho . . Benzaldehyde( 5.42) acetophenone NMR . - , . Benzaldehyde 300-MHz ( 5.42b) 1 ( AA BB C ), (HC, 2H), (HB, 1H) (HA, 2H) . 3 proton n 1 .

B. Para- Benzene , . para- benzene . anethole( 5.43a) .

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5.42 Benzaldehyde 1H NMR . (a) 60 MHz (b) 300 MHz.

(methoxy propenyl ) , proton Ha Ha ( OCH3 ortho) . Hb Hb . . . , proton Hb Ha Ha Hb , . Anethole NMR ( 5.44a) proton 4

5 . 4 3 (a) Para- benzene (anethole) (b) ortho- benzene .

278

5.44 (a) Anethole (b) 4-allyloxyanisole 300 MHz 1H NMR .

. para- 4 . 4 1 . 2 proton Ha Ha ( ), . Proton Ha Ha Jaa . Hb Hb Jbb . Ha Hb(Ha ortho ) Hb

5.45 para- benzene AA BB.

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. JHaHb JHaHb . Hb Hb Ha , . , Ha Ha . Hb Hb . . 5.44a , . , 5.45 4 . AA BB . . 4 para- . 2 ortho , 5.43b ortho- . Ortho- . Ha Hb , para- 4-allyloxyanisole( 5.44b) . . Ha Hb 2 . p-xylene 7.05 ppm .( 5.5) 4 para- . . Alkyl 60 MHz 4 5 .

C. . . Para ortho, meta, para proton . J .

3 2,4-dinitroanisole . 5.46 2,4-dinitroanisole 1H NMR 5.47 . para proton 0(zero). proton nitro . 2 nitro proton HD (8.72 ppm). nitro proton HC .

280

5.48 2-, 3-, 4-nitroaniline(ortho, meta, para ) 300-MHz 1H . Para- 4nitroaniline . 2. 2-, 3-nitroaniline , 1 300 MHz . proton . (s, d, t) . 4J 5J meta para . 2-Nitrophenol 3-nitrobenzoic acid 5.46 2,4-Dinitroanisole proton 5.49 5.50 60 MHz 1H NMR . . proton . Hz . ( 1 ).

5.12 (heteroaromatic) (furans, pyrroles, pyridines, thiophenes ) benzenoid . , furan , furanoid .

5.47 2,4-Dinitroanisole 1H NMR .

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5.48 2-, 3-, 4-nitroaniline 300 MHz 1H NMR .

5.49 2-Nitrophenol 300 MHz 1H NMR proton . hydroxyl(OH) .

282

5.50 3-Nitrobenzoic acid 300 MHz 1H NMR proton . carboxylic acid(COOH) .

5.51 Furfuryl alcohol 300-MHz 1H NMR proton . (CH2OH) .

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5, p. 627 . 5.51 furfuryl alcohol . CH2OH . , ( 1 ). Ha (Hb Hc) methylene(CH2) cis-allylic . 5.52 2-picoline(2-methylpyridine) .(methyl ) , ( 1 ). Pyridine

2-Picoline(2-methylpyridine) 300 MHz 1H NMR proton . Methyl .

5.52

284

5.53 Acetylene allyl (4J).

5.54 Homoallyl (5J).

5, p. 627 . ? Hd . (I 1) , (6.5 ).

5.13 Proton-proton proton . proton . vicinal(3J) geminal(2J) . proton . . Geminal(2J) vicinal(3J) (long-range coupling) . . HC CCH allyl (4J, 5.6 ) meta para (4J 5J, 5.11C). Alkene allyl (5.7) 4J . Acetylene . alkene CH . , NMR . homoallyl (homoallylic coupling) 5 . Homoallyl allyl . 5.53 acetylene allyl (4J) , 5.54 homoallyl (5J) . - . 5.55 meta proton 4J . (furan, pyrrole, thiophene, pyridine ) . furan proton . . 5 proton-proton . Allyl(4J) homoallyl(5J) 23 Hz . furan 3J

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5.55 meta proton (4J).

J vicinal 89 Hz . . . W (4J) W . . . 5.56 .

3

W 4J .

5.56 (4J) W HA HB .

286

. , 4J 1 Hz . NMR . 4 5.57 W ( J) . steroid . . 2 . . W . . allyl (4J 1 Hz) . Steroid methyl decalin methyl W . 5.57 . 4JW . methyl .

5.14

Homotopic, Enantiotopic, Diastereotopic

NMR 2 (geminal ) . Methylene(geminal proton) isopropyl(geminal methyl) .

geminal . Homotopic, enantiotopic, diastereotopic . Homotopic . NMR . Homotopic . , . . , homotopic. 5.58a 2 homotopic methylene . HA HB . homotopic X . 2 . Enantiotopic chiral chiral

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NMR . Enantiotopic . 5.58b 2 enantiotopic methylene . HA HB enantiomer( ) . 2 . 2 NMR . enantiotopic chiral X, Y . 2 . Enantiotopic prochiral . chiral . chiral chiral . Prochiral chiral chiral . chiral 2 . chiral , chiral chiral 6 (6.9). Diastereotopic . NMR . Diastereotopic geminal 2J . 5.58c 2 diastereotopic . HA HB diastereomer . Y* chiral diastereomer . 5.15 .

5.58 Homotopic, enantiotopic, diastereotopic .

288

5.15

Diastereotopic

diastereotopic . Diastereotopic 2 NMR . diastereotopic 2 G G (stereocenter) . G G diastereomer ( 5.58c).2

A. Diastereotopic Methyl : (S)-(+)-3-Methyl-2-butanol , (S)-(+)-3-methyl-2-butanol . 3 diastereotopic methyl . 5.59 5.60 13C 1H NMR .

5.59 13C . diastereotopic 2 methyl methyl 2 . methyl 3 . 17.90 18.16 ppm

5.59 (S)-(+)-3-Methyl-2-butanol 13C NMR (75 MHz).2 diastereotopic, . .

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5.60 (S)-(+)-3-Methyl-2-butanol 1H NMR (300 MHz).

diastereotopic methyl 19.99 ppm methyl . Geminal dimethyl 2 ! Methyl 3 35 ppm, hydroxyl 2 72 ppm . 2 methyl chiral . 2 methyl . Newman . . methyl enantiomeric . .

H proton NMR ( 5.60) . 2 diastereotopic . 2 methyl methyl . 2 . 5.61 . , (R)-(-)-3-methyl-2-butanol racemic 3-methyl-2-butanol S . Diastereomeric enantiomer .

1

B. Diastereotopic : 1,2-DichloropropaneDiastereotopic methyl , stereocenter diastereotopic . Diastereotopic ,

290

5.61 (S)-(+)-3-Methyl-2-butanol 1H NMR .

diastereotopic HA HB , HA HB . 2 proton . HA HB (2JAB). proton HC , 3JAC 3JBC . 1,2-dichloropropane . 5.62 1,2-dichloropropane 1H NMR

5.62 1,2-Dichloropropane 1H NMR (300 MHz).

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5.63 1,2-Dichloropropane diastereotopic proton .

. 5.63 diastereotopic proton HA HB . 2JAB 11 Hz geminal .(5.2B ) ) Karplus .(5.2C ) 3JAC( 180 3JBC( 60 ) HC HA HB 3J(HCCH3) 7 Hz methyl . Methyl HA, HB HC proton

5.64 Citric acid diastereotopic methylene 300-MHz 1H . . Carboxylic acid, hydroxy proton .

292

. 5.64 citric acid diastereotopic . Citric acid . methylene proton Ha Hb diastereotopic . Citric acid . 5.64 proton Ha Hb . Proton Ha OH , proton Hb OH . . C2C3 Newman Ha Hb .

C. Diastereotopic Fluorine: 1-Bromo-2-Chloro-1,1,2-TrifluoroethaneDiastereotopic diastereotopic fluorine . 1-Bromo-2-chloro-1,1,2-trifluoroethane 1H proton 2 . 5.7 ppm 6.5 ppm . 5.65 Newman . 1 proton , proton 3 fluorine( 2 ) .

5.65 1-Bromo-2-chloro-1,1,2-trifluoroethane 1H NMR diastereotopic fluorine .

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*1. NMR . (a) Vinyl acetate( 5.17) (b) Crotonic acid( 5.21) (c) 2-Nitrophenol( 5.49) (d) 3-Nitrobenzoic acid( 5.50) (e) Furfuryl alcohol( 5.51) (f) 2-Picoline(2-methylpyridine)( 5.52) *2. proton (J, Hertz ) , Jab, Jac, Jbc . 5 .

294

*3. Methyl vinyl sulfone . 5.23-5.25 , proton . a, b, c, d proton . Hz .

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*4. Trans-4-hexen-3-one 1H NMR . proton . . proton proton . 3J 4J . a, b, c, d, e proton . Hz .

296

*5. Trans-2-pentenal 1H NMR . proto . . proton proton . 3J 4J . a, b, c, d, e proton . Hz .

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298

*6. allyl(4J) ?

7. dimethyl malonate acetaldehyde(ethanal) C7H10O4 . 1H NMR -13 NMR DEPT . 1H NMR .

Normal Carbon16 ppm 52.2 52.3 129 146 164 166

DEPT-135Positive Positive Positive No peak Positive No peak No peak

DEPT-90No peak No peak No peak No peak Positive No peak No peak

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8. Diethyl malonate bromoethane alkyl . alkyl 1H NMR . .

300

9. C10H10O3 1H NMR . . proton . J . 6.45 7.78 ppm . 12.3 ppm . .

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10. C8H8O3 1H NMR . 8.27.0 ppm . . 12.0 ppm (1H) . .

302

11. C12H8N2O4 1H NMR . 8.37.2 ppm . . . 1352, 1522 cm1 . .

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12. C9H11NO 1H NMR . 9.83.0 ppm . . CH 2720 2842 cm1 . 1661 cm1 . .

13. anethole (C10H12O) anise . NMR . 3.75 ppm . anethole .1H

304

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*14. C8H7BrO .

*15. C5H10O 2.4 9.8 ppm . . : 0.92 ppm(), 1.45 ppm(), 1.61 ppm(). 2.4 9.8 ppm

306

*16. C10H12O3 1H NMR . 12.5 ppm proton NMR . -13 NMR DEPT-135, DEPT-90 . .

Normal Carbon15 ppm 40 63 115 125 130 158 179

DEPT-135Positive Negative Negative Positive No peak Positive No peak No peak

DEPT-90No peak No peak No peak Positive No peak Positive No peak No peak

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17. C10H9N 1H NMR . 8.77.0 ppm . -13 NMR DEPT-135, DEPT-90 . proton . 5 .

Normal Carbon19 ppm 122 124 126 128 129 130 144 148 150

DEPT-135Positive Positive Positive Positive No peak Positive Positive No peak No peak Positive

DEPT-90No peak Positive Positive Positive No peak Positive Positive No peak No peak Positive

308

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18. C9H14O 1H NMR . proton . -13 NMR DEPT-135, DEPT-90 . proton . 5 .

Normal Carbon14 ppm 22 27.8 28.0 32 104 110 141 157

DEPT-135Positive Negative Negative Negative Negative Positive Positive Positive No peak

DEPT-90No peak No peak No peak No peak No peak Positive Positive Positive No peak

310

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19. C10H12O2 1H NMR . proton 12.8 ppm . 3.51.0 ppm . benzene 7.2 ppm . -13 NMR DEPT-135, DEPT-90 . proton . 2.52.75 ppm . .

Normal Carbon22 ppm 36 43 126.4 126.6 128 145 179

DEPT-135Positive Positive Negative Positive Positive Positive No peak No peak

DEPT-90No peak Positive No peak Positive Positive Positive No peak No peak

312

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20. 1-Methoxy-1-buten-3-yne 1H NMR . proton . proton . . 3J, 4J, 5J . ( ) .

314

21. cis trans proton NMR (A B) .(3 phenyl .) . . A 3.68 ppm OH . B OH .

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*22. fluorine (3JHF 325 Hz, 2JHF 4481 Hz). Fluorine19 proton , fluorine n 1 . Proton NMR HH HF . (a) FCH2OCH3 proton NMR . (b) NMR- . FCH2OCH3 fluorine NMR ? *23. C9H8F4O 1H NMR . proton . . 7.106.95 ppm ( 1H) . (1H) . 6.055.68 ppm 1 proton . .(fluorine 5 22 .)

316

24. C2H4BrF 1H NMR . . Hz . .

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*25. DCH2OCH3 proton deuterium NMR , FCH2OCH3 proton ( 22a) . *26. Chlorine(I 2 ), bromine(I 2 ), iodine(I 2 ) geminal vicinal JHX(vic), JMX(gen) 0(zero). . halogen proton proton . BrCH2OCH3 NMR FCH2OCH3( 22a) . *27. H19F proton phosphorus-31 (H31P) . Proton-phosphorus phosphorous phosphonate ester 2J 3J HP 13 Hz 8 Hz. Phosphorus-31 proton phosphorus n 1 . dimethyl methylphophonate .( 5)3 3 5

318

28. Methyltriphenylphosphonium halide methyl 13C methyl 1H NMR . 3.25 ppm , 2.93.5 ppm . 5 9 . . Phenyl .

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29. a, b, c (300.4 amu) . ( .) methyl vinyl . 7.3 ppm CHCl3 .

320

*30. 6 1 , proton .

*31. 6 2 , vinyl proton .

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*32. 6 3 , proton .

Textbooks Bovey, F. A., NMR Spectroscopy, Academic Press, New York, 1969. Derome, A. E., Modern NMR Techniques for Chemistry Research, Pergamon Press, Oxford, 1987. 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, Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2d ed., Pergamon Press, London, 1969. Macomber, R. S., NMR Spectroscopy-Essential Theory and Practice, College Ourline 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, 1959. Roberts, J. D., Nuclear Magnetic Resonance: Applications to Organic Chemistry, McGrawHill, New York, 1959. Roberts, J. D., An Introduction to the Analysis of Spin-Spin Splitting in High Resolution

322

Nuclear Magnetic Resonance Spectra, W. A. Canda N2L 3X2. Benjamin, New York, 1962. NSF-Project Seraphim, University of Wisconsin, Sanders, J. K. M., and B. K. Hunter, Modern has several programs, with information NMR Spectroscopy-A Guide for Chemists, available on: gopher.jchemed.chem.wisc.edu; 2nd ed., Oxford University Press, Oxford, e-mail: jcesoft@macc.wisc.edu: England, 1993. T. Farrar,PC NMR4Windows Silverstein, R. M., and F. X. Webster, J. Swartz,PCNMRandLibrary of Spectra Spectrometric Identification of Organic for PCNMR Compounds, 6th ed., John Wiley and Sons, NUTS, Acorn NMR, demo version from New York 1998. ftp.netcom.com/pub/wp/woodyc; email:support Wiberg, K.B., and B. J. Nist, The @acornnmr.com. Interpretation of NMR Spectra, W. A. Shatz, P., PACCOON,NSF-Project Seraphim, Benjamin, New York, 1962. University of Wisconsin. Yoder, C. H., and C. D. Schaeffer, Introduction TurboNMR, Silicon Graphics Computers, to Multinuclear NMR, Benjamin-Cummings, Biosym Technologies, Inc., 4 Century Drive, Menlo Park, CA, 1987. Parsippany, NJ 07054. WIN-NMR, USA Bruker Instruments, Ins., Compilations of Spectra Manning Park, Billerica, MA 01821. Ault, A., and M. R. Ault, A Handy and (Optional modules include NMR-SIM, WINsystematic Catalog of NMR Spectra, 60MHz DAISY, and WIN-FIT.) with some 270MHz, University science Books, Mill Valley, CA, 1980. Papers Pouchert, C. J., and J. Behnke, The Aldrich Mann, B.The Analysis of First-Order Coupling Library of 13 C and 1H FT-NMR Spectra, Patterns in NMR Spectra, Journal of 300MHz, Aldric chemical Company, Chemical Education, 72 (1995): 614. Milwaukee, WI, 1993. Hoye, T. R., P. R. Hanson, and J. R. Vyvyan, A Practical Guide to First-Order Multiplet Computer Programs Analysis in 1H NMR Spectroscopy,Journal of Organic Chemistry 59 (1994): 4096. Bell, H.,FIDWIN,IBM PC/Windows, Virginia Tech, Blacksburg, VA. (Dr. Bell has other Web sites programs as well, all available from http://www.chem.vt.edu or email:hbell@ WWW NMR Webservers Bruker-Germany chemserver.chem.vt.edu.) http://www.bruker.de/Bruker.html Felix, Silicon Graphics Computers, Biosym Technologies, Inc., 4 Century Drive, NMRFAM, Madison http://gopher.nmrfam.wisc.edu/ Parsippany, NJ 07054. HyperNMR, IBM PC/Windows, Hypercube, University of Florida http://micro.ifas.ufl.edu/ Inc., 419 Phillip Street, Waterloo, Ontario,

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Wilson Lab http://www.wilson.ucsd.edu/education/spectrosc opy/spectroscopy.html Peter Lundberg, University of Umea, Sweden, has commplid complete list of educational NMr software. It is available from a number of sites, including: http://atlas.chemistry.uakron.edu:8080/ cdept.docs/MAGNET/sware.html and the Bruker Web sites. http://www.aist.go.jp/RIODB/SDBS/menu-e.html Integrated Spectral Database System for Organic Compounds, National Institute of Materials and Chemical Research, Tsukuba, Ibaraki

305-8565, Japan. This database includes infrared, mass spectra, and NMR data (proton and carbon-13) for a number of compounds. http://www.chem.ucla.edu/webnmr/ UCLA Department of Chemistry and Biochemistry, in connection with Cambridge University Isotope Laboratories, maintains a website, Webspecta, that provides NMR and IR spectroscopy problems for students to interpret. They provide links to other sites with problems for students to solve. http://www.nd.edu/~smithgrp/structure/workbook.html Combined structure problems provided by the Smith group at Notre Dame University.