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!"#$III
%&'()*+,#$-./00001234567890(5742)
e-mail: [email protected]
:;' NMR<=>?@A?@AB$CDEF
0000GHIJKLMNODEF000
May 30, 2011
June 23, 2011
P9 QRSO<=>2) 1H NMR?TUV9 #$WXJOY: Z[T\?Q\]^_`9 #$]abcdOY'efgaEh?i) j<klmnf'Z[?op9 IqrsIqrtuvw'xyZ[O?z{|9 13C NMRlmnf
<\Yn}m~?�!?��BDE5����s?�\#9F����s?��l�����5�U�9?�#Bh��DF(pp421-423)
<=�K��B��DEF<=�Y��aS�?=���DE��l�~}� DE¡O�K¢E (CW<=�9F
£¤�¥¦B§¨sDEQRS©�IBwnEª>(FT-NMR)
Fourier�«
<\�!?����s?¬K�¡E��?®¯I°±J�B²E¡O�K¢EF
X³, ´µ³, ¶·=, ¸µ³, ¹º±»S, ¼½¾S5¿Iqr?ÀÁ9
Q\ÀÁ':ÂQ\BµÂÃ?ÀÁÄÅ]lY¯ÆÇdÈÉ~�ÊÆÇdÈÉÃ?ÀÁ
QRSO<=>
1H NMR?TU
¿Iqr'T\¿�ËDÄm?ÌBÍÎlÏÐDEdÑ?¡OF
!ÒÓO"ÒÓ?����sÔlÄÕDE����sBÖm×S
o?¼½¾S����دÙÚ5ÛÜ]a��OÝÞ9��¡EF
1HßµlNMRà±Háâaãä
å æ»JrYçQèfnE?K¯ÏÐDEORéBê�E5ëìÍ?Rí9å µîRéOï�ð¢?ñòB!IqrÒÓ, óð¢B"IqrÒÓ(p425)
å ����sÔYôõ?ÒÓKYG�}¯ö�÷¹r<ølù¢aÔ�anFå µîRé��núû¯����sÔ�ù¢nF H
0 = 70,500 G ?O¢¯Z[¿?ÙÚ¤�oY 300 MHz0(± 3000 Hz)F
*#$WXJYµîRé?ù¢�l��ü¯ï�ýOaE5þÿ9F
å ¿äl��f¯��S�?¥¦�!aE5®10-6, 10-79F
å "\#�YÍd\�$o?¿äYNMR�%'1H, 14N, 19F, 31P or 13C
å "\¯Íd\�Ohl&o?ãäYNMR'(d'12C, 16O
å )*+,k�-nãäY./�Ø0DnF
Z[?#$WXJ
1<23NMRKY¯<\?ãZ[B45DE¡O�K¢EF
¿��6Ho?Rél~ØEO¯7ØB89:D��l¿?×;
?Q\Y<=RéHlocalB>êDEF ®10-9
?@?I°±J�KY…5®10-119
ãZ[?Q\A6�!aE�BlµîRé?z{lCn�ê�EFå ÆÇ?Dd, ÆÇèfnET\?EFå «@?ÙÚG�HI�JK
å LÃn��n¿05Q\A6�1n90!01RéM5I°±J�NM9å ÊLÃn�ØfnE¿5Q\A6�On90!0ORéM5I°±J�?PM9
å Z[¿?Q}?£Ré�6YRSDEF0!0LÃn#(Shielding)
å Q\A6?ù¢a¿Y, LÃnJK�ù¢nFå ÊT?UVh�¡;�EF0!0ÊLÃn(deshielding)
#$WXJ?WèX
YZa¤�o5[V\\\Hz :9B]BE�;¯:î^_O?tT]aý
Oèf/`DEF
aBmbanOnban¡OY…
µîRé?�6lc+èfÙÚ¤�o��dE5keDE9F!0^_#' (CH3)4Si ~�?fg5¤�o?Ô9B<=�?¤�oKhEF
^_�Ñ'0HJ¼ij�W¼r [ (CH3)4Si ]?��B \ Hz ODEF HJ¼ij�W¼r?ij�@YQakd6?G�nW
00000000lmrlÆÇèfnE?K¯ôõ?!"#Ç�?Z[00000000�;Q\A6�1nF!0n?qs±~�gØfnEF
! = qs±?(CH3)4Si ~�?fg (Hz)
<=�?¤�o (Hz)ppm
RéO¤�o?op
#$WXJYq3@lrs]
W10-2 O 10-3:0×tu,O#$WXJ?op
å LÃn��n¿05Q\A6�1n90!01RéM5I°±J�NM9å ÊLÃn�ØfnE¿5Q\A6�On90!0ORéM5I°±J�?PM9å vjJKå ÊLÃnJKYfgOÙlRSDEF
e'0 ÊLÃnJKYfgOÙlRSDEF0000wxâ»y滩r, 1-â»y滩r0(p432)
#$WXJ?¬ LÃn?z6 q3@?ä{
|}'~r�r?Z[Y�[lÆÇèfnE?l¯a�ORéWXJèfnE?~�Qakd6l��f¯©ºÆÇ?^Q�JKl�ERa!Xd�z{DEF
#$]bcd
�#$]lbcaZ[?qs±Yï�#$WXJBhmF
�C��10-5
���ñ�?�«�NMR?��I�s�KY0nF
ÏÐO��
å /��QKY��#�Ø�qs±B��EFå O��K<\?�¢B�}5�Æ9DØ�¯gbcaZ[B./K¢E0 éÇh�EF
<<1 sec
j<k
�1H NMR KY¯qs±?�jkKæ»Jro5Z[?o9?kB
00�`K¢EF
å �jkY¯��"Kqs±�³:M?j<l�;]B�ØE?K¯ôõj<kOn�Få0e��¯®10-15
�C��10-6
Me : CH2 : OH = 9 : 2 : 1
å D f?¿äK¯j<k�¿?olkeDEdbKYanF
A: `m?Z[YD fbcFB: j<k02:1:1
C: j<k01:1
A B C
bcG�HgbcaZ[?45�¡¢F
gbcaxyZ[?z{
� gbca¿�xyDE5ôõVÆÇß:K90 O¯xyDEZ[?z{KhOhO?Iqr�
00<£DEF
� xyDEZ[¤Oml�¥f¯W¦§��
00¨©³l<£DEF5ª9
� xyDEZ[?ol��f¯<£?z6�1
00#¥fn}F5¸9
!0IqrxIqrÆÇ05IqrxIqr<£#�Ytuvw9000Z[¿?!ÒÓO"ÒÓY/��QKú«1:1K�E¡Ol¬DEF
bcaZ[¿û�èYGunl®?z{h��anFè~èa��gbcaéÇ…
Gunltuvwèf¯W¦§�lù¢a�#Bh��DF
®P\xPp5p4409
a�<£DE?~�
®10-17 O ®10-18
H0
+ h H0
- h
5.36 ppm
4.39 ppm
�qs±�?fg5§¯ælr¦`o9Y0 unlbènF
�§¯ælr¦`oY¯#$WXJ?Ôl0 <=�?×SoB~b�h?
��¥f¯§¯ælr¦`oYµîRél0 °opK�EF
5.36 ppm 4.39 ppm
Jab
= 7 Hz Jab
= 7 Hz
û¡#K§¯ælr¦DE?~�
� ½±²§�§¯ælr¦
� ³W§�§¯ælr¦
ï��[lÆÇèfnEéÇù¢a§¯ælr¦`o5´P2 Hz)
xyDE�[lÆÇèfnEéÇôõ¯§¯ælr¦`o0[µ Hz
� bca¿û�èY§¯ælr¦èanF
Ethane: 0.85 ppmlĶ³?·./�ØEF
¨m߸?Z[O?IqrsIqr<£-1
�!!"#"$!¹ !"#$"%&?º»¼
®'()*'+&â»y�½r?e5!,,,9
��d��E
qs±�jY�d�anF
¾Ï?¿C
�C�� 10-8 <\ÀC5H12O?à�ms�#�Y�sH�
P446, W10-5
å IqrxIqr<£YQ}?gbcaZ[?�K�¡EFå Z[?��Y¯ N Á?bcaxyZ[l�¥f N + 1¶l<£DE05N+1¹9Få <£qs±?tT�6YPascal?º»¼lË�ØEklaE5��d9F
! = 0.93 (t, 3H)
0001.20 (t, 3H),
0000001.60 (sextet, 2H),
0003.37 (t, 2H)
0003.47 (q, 2H)
0
#$WXJ'�[lÆǯij�§¯ælr¦'bcaZ[�¨mxyF
#$WXJ'�[lÆǯijÂr§¯ælr¦'bcaZ[�ÃmxyF
OH ?PH �anF!0�sH�
[ppm]
#$WXJ'Ä[lÆǧ¯ælr¦'bcaZ[�¨mxyF
#$WXJ'Ä[lÆǧ¯ælr¦'bcaZ[�ºmxyF
�C��10-8
¨m߸?Z[O?IqrsIqr<£-2
ÅÆae5p4479: U?]lYN+1¹lÄÕèanéÇ�-nF
P9#$WXJ�QnéÇ5#$ ~ J9: gÄÇ000000000000000000000 ÈÉa N + 1¹lÊdanF00®10-23'¾±½r?e00®10-24: µîRé�ù¢bØ�¯<23�ð¸F
N+1¹BÛÜ]lËwDE¡OK¯Hb?<£©½srBU2K¢EF
w9gbcaxyZ[�+,DEéÇ
! = 1.69 ppm (d, J = 6.8 Hz, 3H))
0004.35 ppm (dq, J = 3.6, 6.8 Hz, 1H),
0005.86 ppm (d, J = 6.8 Hz, 1H), 000
Ha: xylÄm?Z[�;FÊLÃnJKKORéMFHb: bcaZ[VmOgbcaZ[PmFHc: xylÄm?Z[�;F
®10-260
¨m߸?Z[O?IqrsIqr<£-3
ÅÆae5p4509
gbcaZ[O?§¯ælr¦a?l¯NÌP¹lÄÕDE��lÍ�E
éÇ��EF
®10-27
Hb
HaOHcY¯unlgbcaYüF
HbY¯Hal�Eº©³?Hcl�EΩ³K¯Pw¶�
00ÏÐÑÒ©³05®10-289
a�a��
§¯ælr¦`o�efnE�B¯-}?³�©a;¯<£©½sr�ÓÔ#
cf. �C��10-8
Õ§¯ælr¦��¡EéÇ
®10-11CH2Y¨©³�Ä©³YG~èn?KY�Ä©³laEU¬Y…
ZÄ@?æ»Jr�¯NMR?��I�s�KÖ:?Z0ÄO?�K
×<lØ}Á�èfnE�B¯W¦§����#�ØEF
D�0næ»JrÙ«l�;Õ§¯ælr¦�ØfnEF
®10-29'i½Ús�?eè~è¯æ»JrÙ«B�}DØ�¯§¯ælr¦?./�¶3F
å0Z0ÄBÛ}Få0O�K/`DEF
ÜÝÕ§¯ælr¦
Þ»ßrYRdBhm�¯X¯[ßµY?Ñ]l§¯ælr¦èanF
!NMR��I�s�KØnÞ»ßr?Ra�à��E�B��#�د0 µîRél�EÔ�ê�l}nF
½àIH¾Jq¯±aZ[?gbcd
ijÂr?Z[Y¯?Y!aE^_l�EéÇ�-nF
ijÂr?Z[Bn?«@l¢«�EO½àIH¾¹s�ê�Eéǯ½àIH¾Jq¯±K�EOn�F!0gbcaZ[
P. 452, Þº¼ºJ10-3
áÒ?<\Kh¯â¼�ÍÎBÖf�'ãNlQnijÂrY½àH¾Jq¯±laEF
13C NMR
NMR(da�[513C9Y¯)*ldü~1.11%è~+,èan
13CY12Clä#ØfnE~�¯�[x�[IqrÆÇBåb�ØEF
æ6�O}aEFI°±J��ÈÉ#�ØE
a�a��¯
Z[?O¢Oï�TUl�;¯�[?NMRh/`¶3K�EF
å0#$WXJ?çä�ù¢nF[è00 ppm
0 0 å0j<kY¿?olT�èanF
è~è¯+,k?ù¢nZ[O?§¯ælr¦l�;ÅÆlaEF(®1-30)
Ca: Z[O?º©³5G9OΩ³5ù9Cb: Z[O?º©³5ù9OΩ³5G9
Z[BÕ§¯æ�èfÈÉ#B®E
û?��lèf¯Z[BÕ§¯ælr¦�éE~�00000
13C: 62.8 MHz1H: 250 MHz
13CI°±J�B/`DEO¢l¯
Z[?ÙÚ¤�oB§¨sDE�êaÄ`ë?¼½¾SBìíèÜbEF
!ÒÓO"ÒÓ?IqrÊÐ�D�0}�¡;¯
ÆKOèfZ[Y��#�ØfIqrsIqr<£K¢a}aEF
! Z[O?§¯ælr¦�2:�د0013CYÄ©³ÃOÈÉ#�ØEF5®10-329
ÆKOèf¯�6hîï�ØEF
®10-30O®10-VPBkðF
ñò¦æ»JrÕ§¯ælr¦
�[?#$WXJhq3@lT�
WP\xp13C NMR?#$WXJ'0
00000000u,]a^_5q3@9l�Ers]a#$WXJBËDFQ\] d@0!0ÊLÃnÄó0ô0¨ó0ô0ºó©ºÆÇl�E^Q�JK5Ra!Xd9!ÊLÃn
13C NMR?j<'00�[¿?oOkeèanF0
gbca�[?o0!0<\u,?2õl!w
�C��10-12
4
4 3
1
16a/`
(A) ñò¦Õ§¯ælr¦I°±J�(B) DEPT-90 'PÁ?Z[�ÆÇè��[5CH9(C) DEPT-135: CH3OCH0!0Y?Xð00000000000CH20000!0ö?Xð
÷Îó00 !0Lan
13C DEPT
toNMRI°±J�
¨ÇøNMR: §¯ælr¦ènfnEW¦§�?±»Iqs±5to9B./DE
Z[O�[?ùúl!w
1H-1H COSY 1H-13C COSY
Þº¼ºJ10-5 u,�`