ベンゼン環を含む - coocantakahiko.life.coocan.jp/univ/2012/121107_25_aromatic.pdfoh ona naoh...
TRANSCRIPT
49
2012ÛÝ�¨Íœ 25¿ (óáƮƓÖ ƪâ)
n|W|IJA¸6ĊĔ¨´Į
FEC ��t�-f�`��,C
Ō�!+��),ƬÔ(�ųŐ8"$8 2�ŏƦ+ŬĿž�ÌÁ�$�<ƬƁ�+đìčĀ&�$Ƭ4�Ƭij¨Í°è+ŶÊ&�$Ƭij»İż)ġ�ƚ
@"$�=ƭŌ�!+��)ÌÁ�=ŬĿž+ÂČƩĐ,Ƭ�1$ 20ŏƦ+DtdƐ):"$ŗ5ő$;>$�=ƭ�>; 20 ŏƦ+DtdƐ+�!Ƭ3ŏƦ),n|W|IJ�¸4>$�=ƭ
n|W|IJ,4�ƬªŪ½+ÂČƩĐ&�$8ĵ�;>$�=ƭ��)ŋ
� 3ŏƦ+¨´Į,Ƭ��>8Ɨļ¤&�$ĵ�;>$�=8+%=ƭ
�;)n|W|IJ,ƬƁ+¹<+rxs~+�)8¸4>$�=ƭo[_
q_y+ŕč%=rxHZz|]zkYz~_(PET)9ƬQ|ibH|UU_D%ŽÆ�>$�=Þá+ƆąkY)ĵ�;>$�=rxUZz|(PS))
O
O OH
O
CH3
H3C
CH3
CH3
O
OH
CH3
O
OHO
����� �� �� ����
C CO O
O O
CH2 CH2n CH2 CH n
������� �������� ���������
NH2
OH
O
NH2
OH
O
HO NH
OH
O
NH2
������� � �� ������
50
,Ƭn|W|IJ�¸4>$�=ƭ�+:�)n|W|IJ,ƬĒ�(ĊĔ¨´
Į)¸4>$�=ƒŲg~\+�#%=ƭ�¿,�+n|W|IJ+��5
&êž)#�$ıŵAġ7:�ƭ
GEC ��t�]�B';C
n|W|, C6H6%;@�>=Ī¨ěŕ%=ƭ�+�Ë, 6 �+ĪŕË�;ì=�äDyJ|�x|N)("�đƈA8"$�=ƭ�+�7Ƭ
n|W|A;@�đƈß&�$,Ƭ��+(a)%8(�(b)%8(�Ƭ(c)+:�(8+�/�@��&8Ş ;>=ƭÑƝƬ6 �+ C�C ř´+ƀƟ,��>8Ŕ���&�@�"$�=ƭ
(c)+đƈ,Ƭ(a)&(b)+ƒ*´@�&ıŵ�=�&�%�=ƭ#4<Ƭn
|W|�Ë,Ƭ(a)&�$+êž&(b)&�$+êžA�>�>Ŕ��ŋ��Ë%=Ƭ&��Ş ĂA�=�&�%�=ƭŷ�û =&Ƭ(a)8(b)8�>�>n|W|+êžAƍ�ŀ);@�đƈ%=&Ş ;>=ƭ
�+:�)Ƭn|W|A;@�đƈ(a)&(b),�B';&º->=*1ƭ�
ş+ƚ�,Ƭ(a)&(b)&Ař0�ƥҬ %;@�>=ƭ
�ƫđƈ,ƬË+zEDF_,�+44)ƬË&ËAř0ř´Aŗ
5Ĉ �8+)("$�=ƭř´+ŗ5Ĉ AҬ):"$;@�&Ƭĕ
+:�)(=ƭ 1 �ƫđƈ)#�$,�ƐŕA¸6ĊĔ¨´Į+�Jyqby¨´Į%8ï"�ƭlx|_ 39o~T®Ĭƭ
C
CC
C
CC
C
CC
C
CC
(a) (b)
H
H
H
H H
H
H
H
H
H H
H
C
CC
C
CC
(c)
H
H
H
H H
H
C
CC
C
CC
C
CC
C
CC
H
H
H
H H
H
H
H
H
H H
H
51
n|W|IJ,Ƭĕ+:�)Ņķ�$;@��&�È�ƭ
(a),Īŕ 6 ��;ì=x|N)�ơË�Ŕ���Ċ�>$�=�&Aŋ
�;@�Ă%=ƭ(b)�:.(c), 2ŏƦ+�ƫđƈ%=ƭƇÙƬ�>;3ŏƦA©¢�=�&(�ĵ�$�Ë+đƈA;@��&�È�ƭ�& -n|W|+ěŕ H� 1�Ƭh`{KS –OH)ŝû�>�¨´Į(kGd~y),Ƭĕ+'+ĂĞ%;@�$8Ŧ�ƭ
HEC ��t���]P?�C
n|W|�ËAđì�= 6�+ĪŕË C,Ƭ4�+�ơË+�! 2�%�ƞ+ C&Ƭ1�%ěŕ H&Ƭ�>�>�ř´�$�=ƭė< 1�+�ơË,�ř´)ĵ�;>$�=(À 1a)ƭ�>; 6�+�ơË,įÐ+ C)îÕ�$�=@�%,(�Ƭ6�+ C):"$�Ċ�>$�=ƭ�+řĎƬ6�+�ơË,n|W|�Ë+x|N+ůűAŤĶ)Ü�=�&�²Š&(=ƭ�(
@!Ƭn|W|�Ë+ÌÁ�=ÚƢ,Ƭ�ơËƠ):"$÷4>�đƈ&("
$�=(À 1b)ƭ
�+�ơËƠ�Ƭn|W|+°èêAĜ7$�=ƭ�(@!ƬsEaU+
ơŨA8"�ƠAô#�&):"$Ƭn|W|,lwU+ơŨA8#EI|
A#�4 9��(=+%=ƭ
C
CC
C
CC
C
CC
C
CC
H
H
H
H H
H
H
H
H
H H
H
= =
(a) (b) (c)
= =
OH OH OH
52
IC��t�[|�n�[]� C
DyJ|)e{P|A°è��=&ƬwTJy°è):"$ěŕ&e{P
|&��>Ĉ@=�&,�%)ÍB ƭ4�ƬDyO|)e{P|A°è�
�=&Ƭ�ƒř´)e{P|��§�=�&8ÍB ƭ%,Ƭn|W|)e
{P|A°è��=&'�(=+ ?��? °è+��Ă� 2Ƈ<=+%Ƭ�>�>)#�$ų$ŭ��ƭ
!�
!� !�
!�
!�!�
"� "�
"�"�
"� "�
!�
!� !�
!�
!�!�
"� "�
"�"�
"� "� #���$����
%&'� %('�
� ��������� (a)ĪŕË C '��+ř´Ƭ�:.ĪŕË C&ěŕË H&+ř´ƭ6�+ C& 6�+ H,µ�ÚƢ�)ÌÁ�=ƭ�,�ř´)ĵ�;>$�=ơËƬ�,�ř´)ĵ�;>$�=ơËA;@�ƭ(b)6�+�ơËAơËƠ&�$;@��ôƭn|W|�Ëx|N+ÚƢA���;ơËƠ�÷B%�=ƭ�+��+ơËƠ),´Ÿ 6�+ơË��Ċ�>$�=ƭ
CH3 HCl2
CH3 Cl + HCl
CH2 CH2Cl2 CH2 CH2
Cl Cl
Cl2 ?
53
IEFC7����\RUd|�n�\bd2#� C
n|W|&Åŕ Cl2AĢ´�Ƭ��)ƕ Fe A§ $5=ƭe{P|�ƔÕ&ħ��°è�=�&,£ċ)ÍB ƭ�+°è,ĕ+¨Í°èß%;
@�>=ƭ
2Fe + 3Cl2 → 2FeCl3
�;) FeCl3,Åŕ&°èAś�=ƭ
FeCl3 + Cl2 FeCl4– + Cl+
��%ij�= Cl+�Ƭn|W|+�ơË)ùø�>=ƭ��$Ƭn|W|
�Ë�+ H&ŝ�û@=ƭ�(@!ƬƕŶÊÌÁ�)��$e{P|&n|W|&,ŝû°èAƊŭ��=ƭ
�(@!Ƭn|W|&e{P|&AƕŶÊ+ÌÁ�%°è��=&Ƭĕ+
:�(°è�Ɗŭ�=ƭ
Cl2+�@<) Br2Aĵ�>-ƬC6H5–Br�æ;>=*2ƭ
IEGCiz�l�\bd��t�_]|�n�� � C
ƕŶÊAĵ�=�&(�Ƭn|W|&e{P|&AĢ´��å)�Hcy
L~A� =&Ƭ��+:�(�§°è�ij�=ƭ��%ij�=n|W|m
KRM{x`(BHC),Ƭęū¤&�$Ƙ�ĵ�;>$��¨´Į%=ƭ
2 F2& I2+ô),Ĺ(=ĂĞ�ĵ�;>=ƭ
HC
HCCH
CH
CH
HC
Cl+HC
HCCH
CH
CH
HC
HC
HCCH
C
C
HC Cl
H
H
Cl
HC
HCCH
CH
C
HC Cl
H+
H+ + FeCl4- HCl + FeCl3
+ Cl2 +HClFe
Cl
54
JEC ��t�]8��C
JEFC�3�f F ��WYa]C
n|W|)ÏŠÂA 1� �Ó���¨´Į&�$,��+:�(8+�=ƭ�>;,ªŪ½9ªĽčĀA´ì�=Ɲ+�ľčĀ&("$�=+%Ƭ
¶ŎAŴ $���ƭ
_yH|,Ē�(ĊĔ¨´ĮAĦ��Ħ¤&�$Ü�ĵ�;>$�=ƭÄ
Ā9úņ¤+ØƑ)ĵ�;>=ƭ¦Į)õÐ�>$�=ƭ_yH|AƐ¨�
=&ÎëƨƐ�æ;>=ƭÎëƨƐ+a_xFuÅ,�ÌĀ&�$ƧĀě)
ģ§�>$�=ƭkGd~y+ØũěĦĠ,ƬğĚŪ&�$ªĽĔƚ%ĵ�
;>$��ƭ¦Ū%=ƭUZz|,rxUZz|(PS)+Ā%=ƭn|W|Uyp|ƐƬb_{n|W|ƬDbx|,Ƭ�+¨´ĮA´ì�=�7
+�ľĮž%=ƭ�& -b_{n|W|Aƌ��=&Dbx|�æ;>Ƭ
Dbx|AčĀ)DV_Dbx`A´ì%�=ƭDV_Dbx`,�£Ƭŵ
ĭƗļ¤&�$ĵ�;>$��Ū½%=ƭ
OH
SO3H NO2 NH2
COOHCH3
NHCOCH3
���� ����
��������
�����
������ ���� �����
HCCH2
����
+3Cl2
H Cl
Cl H
HClH Cl
ClHCl H
hν
55
JEGC�3�f G ����WYa]C
n|W|IJ), 2���+ÏŠÂAÓ��=�&�%�=ƭ�& -��+ªŪ½��&�$ö�;>=ƭ
RxZyƐvZy,ğĩƗļ¤R{vZ~y+�ì�%=ƭDVZyR
xZyƐ,ƥļŪDUjx|+�ì�%=ƭfkCx|+�ì�%8=ƭ
�ş&8RxZyƐ�;´ì�>=ƭ�+RxZyƐ,kGd~y�;´ì
�>=ƭ
n|W|IJ) 2�+ŝûÂAÓ��=ƝƬŝûÂ'��+ńÒŀ(�ŝƚ�� 3 gY~|ij�=ƭ�& -�CH3&–OH AÓ���ô),ĕ+:�)(=ƭ
o–Ƭm–Ƭp–,�>�>Iy_ƬvYƬgw&ź6ƭ�Qm�u��,ªĽĔ
ƚ%ğĚŪ&�$ĉƅ4%ĵ�;>$��ƭ��>8Łţ)Ŷ>=&ĩĻA
ſ��ƭ
��������� ����
O
O
CH3
���������������
OH
O OCH3
O OH
�����
OH
O OH
������
CH3
������
CH3
OH������
OH
H3C
OH
56
KC/)Sc%.,9f�d�5A$��,]��C
ŧƨĄ¨´Į+É«,ňĝAĀ)´ì�>$�=ƭňĝ�)¸4>=�
Ų(ŧƨĄ¨´Į,n|W|Ƭ_yH|ƬKSz|(o–Ƭm–Ƭp–Ĺê�+Ģ´Į)%=ƭ�>;A4&7$ BTX&º0
KEFC ��t�Scrv�yXdC
�ŝûn|W|),ƬŃú´ì%�=8+&Ƭ2 ĘƜ��+l{VUAŘ(�>-´ì%�(�8+�=ƭn|W|�;UY~_�=´ìy~_+
�A��)ŋ�ƭ
CH3 CH3
CH3
CH3
CH3
CH3
CH3
NO2 NH2 NHCOCH3
CH2CH3 HC CH2 HC CH2
n
/-:3;); #/7; #(-#5.
3;); '*9; 47'*9;
CH CH3H3C C CH3H3C
O2H
OH
1$0<8
����������!" �
���26'*+& ��
����=���!���
�� %',8�
��
�
���� ��
57
��%´ì�>�kGd~y�;,Ƭ�;)ĕ+:�(¨´Į�´ì�>
=ƭ
KEGC y�i�Scrv�yXdC
�ĂƬ_yH|�;,ĕ+:�(¨´Į�´ì�>=ƭ
OH OH
COOH
OH
COOCH3
OCOCH3
COOH�� ��
�� ��� �
� ��� ������
�����
�����
CH3
COOH
CH3
CH CH3H3C
CH3
CH3C
OOH
CH3
CH3
OH
�����������
��������� �
���� ��� ��
��
58
KEHCkq��Scrv�yXdC
4�Ƭp–KSz|�;,ĕ+:�(¨´Į�´ì�>=ƭ
KEIC ��t�Sc~h{��fZTdC
kGd~y,Ē�(ªŪ½9ƪ�ËčĀA´ì�=Ɲ+�ľčĀ&�$
ƒŲ(¨´Į%=ƭn|W|�;kGd~yA´ì�=Ɲ),Ƭ–OHÂAn|W|IJ)ŃúÓ��=Ñĵŀ(ĂĞ�ī��7Ƭm��*&º->=ðŮ
Aĵ�$ijĴ�>$�=ƭ
Mv|Ğ,ƪď¨Í+ÿōć)8ƃ"$�=+%Ƭ'+:�(��5)
("$�=+�ĺ¾)é"�ş8�=�& ?�ƭ��%�¿,Ƭ�+°è
+��5Aų$5:�ƭ��),Ƭ�>4%)ÍB%��ĊĔ¨Í+ŻŲŕ
�ŗ5´@�"$�=ƭ
�+°è+œ�ĘƜ,Ƭl{jz|&ƐŶÊ&+°è%=ƭ
+
OH
+O
��� ��� ����� ����
CC
H
H
H
H3CH
OH
H
H3CCH
CH3 OH
H
CH3
CH3
COOH
COOH
CC
O
O
O
CH2CH2 O
n�������� ��������
�����
�� HOCH2CH2OH
59
��%ij��ƬĖơŨA8"�Ī¨ěŕ[CH3CHCH3]+EI|�Ƭn|W
|&°è�ƬMv|Aij�=ƭ
ĕ)Ƭ�+Mv|�ĭ):"$wTJyƙŰ�=ƭ��$Ɛŕ O2&°è
�=ƭ
�+�Ë� 2 �ł+Mv|&°è�$Ƭěŕ H Aà�ñ�ƭ�+ĘƜ,
wTJy°è+ƉƖ°è%=ƭ
H Aà�ñ�>��ß³Œ+wTJy,Ƭ�Ę£)í"$Ɛŕ O2&°è
�Ƭ�;)ĕ+Mv|�; HAà�ñ�ƭ�+Mv|h`{oyIKS`,H3O++þüA±�=ƭ
H3CCH
CH3CHH3C CH3
HO
H
H
CH CH3H3C
HO
H
H
���
CH
H3C
H3CCH3C
H3CH
O2
CH3C
H3CO
O
C HH3C
H3CC
H3C
H3CC
H3C
H3CO
O
+
CH3C
H3CO
OH
+
����������
60
Mv|h`{oyIKS`, H+Aù4 $ H2OA�<Ɵ�ƭ�+&�):�� �ij�=*3ƭƂ�°è&,�Ë�%Ë&Ë+#(�<Ă�Ǩ�Ƭ
�Ë+ƩĐđƈ�Ç@=°è%=ƭ��%,n|W|IJ,ĉ ) C Ë&#(�"$���Ƭ����>$Ɛŕ O&#(�<Ń�$�=ƭ
ĉŖĘƜ,§ě�ŵ%=ƭ�+ĘƜ�Ŗ@=&ƬłŀĮ+kGd~y&Ƭ
¥ijìĮ+DV_|Ƭ�;)ƐŶÊ H3O+�ij�=ƭƐŶÊ H3O+,�Ɖ+°
è+ĉ +U][l)í=ƭ
3 ĊĔ¨Í°è,ŝûƬ�§ƬŢƟƬƂ�+ 4gY~|)�Ʀ%�=�&A�%)ÍB ƭ
CH3C
H3CO
OH CH3C
H3CO
OH
H
OC
H3C
H3C H
OH
OH H
H
����
����
OH H
H
OC
H3C
H3C OH
HO
CH3C
H3C O
H
H O HH
OHH3C
C
CH3
O
����
����
61
LC ~h{��Sc�"Ved%.��,C
LEFC ~h{��Scp�w�>fZTdC
kGd~y�;RxZyƐA´ì�=ĂĞ&�$,Ƭo���q��xy�
&º->=ĂĞ�ĵ�;>$�=ƭ�+��5Aų$5:�ƭ4�ƬkGd~
yA NaOH&°è��Ƭa_xFukGdKS`&�=ƭ
a_xFukGdKS`A 10 MPaƬ125 °C%�Ɛ¨Īŕ CO2&°è�
�=&Ƭ–OHÂ+ o–�)��$ŝû°è�ij�=*4ƭ
RxZyƐ+a_xFuÅAƐ%�¼�=&ƬRxZyƐ�æ;>=ƭ
4 –OHÂ,Iy_}gwƎ·ê(+%Ƭp–�)��$8ŝû°è�Ɗŭ�=+%,(��&ĺ¾Aô#�8�>(�ƭ���Ƭ�+°è)��$, Na+
� CO2A o–�)Ó��7Ƭ2&B'� o–�%°è�=ƭ(�ƬNaOH+�@<) KOHAĵ�=&Ƭŝû°è, p–�%Ɗŭ�=ƭ
OH O Na
NaOH+H2O
ONa
���������
ONa
OC
O
OH
C
O
O
OH
C
O
O
Na
Na
����������
OH
C
O
O HO
H
H
OH
COOH
+H2O
�����
62
LEFEFCp�w�>Scp�w�>�w�fZTdC
RxZyƐ+–COOHÂ)vZyHU]y¨Aă�$æ;>=¨´Į�RxZyƐvZy%=ƭ�+°è,�ťŀ(HU]y¨°è%=ƭ
LEFEGCp�w�>Scgsw�p�w�>fZTdC
RxZyƐ+–OH ÂAƏƐHU]y¨�=�&):"$æ;>=¨´Į
�DVZyRxZyƐ%=ƭ��%,RxZyƐADyQ~y&�$ĵ�
$�=ƭ�+°è,ƏƐ&+°è%,(�ƬīěƏƐ&+°è%=ƭ
°è,īěƏƐ&Ɛ(ĨʼnƐ)&+°è�;UY~_�=ƭʼnƐ,ŶÊ&�$�ĵ�=ƭ
��)RxZyƐ�DyQ~y&�$þü�$�=ƭ
OH
COOH CH3OH+H3O+
OH
COOCH3 + H2O
����� ����������
O CO
CH3
COCH3
H O CO
CH3
COCH3
HO CO
CH3
COCH3
H
HO C
O
CH3
CO
CH3
HO
COOH
OC
H
H3C
HO O
CCH3
OCOOH
OH
H
63
LEGC ~h{��(4C
kGd~y&pyuDy^h`&AŶÊÌÁ�%ƒ´��=&ƬkGd~
yēš(n~MwE_)�æ;>=ƭkGd~yēš,§ĭ):"$Ŋ¨�=+0�!(4%=ƭÎ�%ŚŜê)�>=ƭƁƅ(&�?%,ơĤQ|V|
_)×�Ƅ6t\sY)ĵ�;>$�=Ŋ�ēš�n~MwE_%=ƭ
OC
H3C
O COOH
OC
H3C
O O
C
CH3
HOCOOH
HH2O O
C
CH3
HO
H3O+
���������
��
OC
H3C
HO O
C
CH3
OCOOH
OH
HH
OC
H3C
HO O
C
CH3
OCOOH
HH2O
OH OH
OH
64
MC2#��&C
�%)n|W|IJ)Ó��>$�=ÏŠÂ�Ƭ2 �ł+ŝûÂ+Ó�)¯3�ãƣA2#��&&º0ƭ2�ł+ÏŠÂAIy_4�,gw�)Ó��=êžAj�yQ}�=�!ƬvY�)Ó��=êžA�v=�!&º0ƭĒ�
(ŝûÂ+Ǝ·êAÀ 2)ŋ��ƭ
Iy_-gwƎ·ê+ŝûÂ�Ó��>�n|W|IJ) 2 �ł+ŝûÂA
Ó��=&ƬƇÙ,Iy_�&gw��µĆ)ijì�=ƭ�+�7Ƭ�şA
�Ɵ�=ý��çŲ)(=ƭ
MEFC��,�"��y]<�C
�4�4(¨´Į�n|W|IJ)ŝûÂA 1��#Ó��$ŭ�ĂĞ%´ì�>$�=ƭ�+&�)ŝûÂAÓ��=ƤĸAŞ (�&Ƭłŀ&�$
�=đƈ+¨´ĮA´ì�=�&�%�(�ƭ
�& -n|W|�;RxZyƐA´ì�=y~_,��+(a)(;²Š �Ƭ(b)%,�²Š%=ƭ�>,Ƭ–COOH �vYƎ·êAŋ��;%
=*5ƭ
5 Iy_-gwƎ·ê(+%Ƭ(a)%,gw�)ŝûÂA8#¨´Į8´ì%��� �ƬƎ·ê&,Ĺ(=ıĶ%Ƭ�+¨´Į)ƛ"$,Iy_�AƋò
ŀ)´ì%�=ƭ
NO2
SO3H
C
CH
O
OH
OC N
N+R3 C O
O
CH3
Br
F
I
ClC CH3
O
CH3
OCH3NH2
C6H5
HN C CH3
O
OH
���� ������
� GC C2#�]�v=�!Rb^j�yD}�=�!�vYƎ·êAŋ�ŝûÂ�Ó��>$�=n|W|IJ) 2 �ł+ŝûÂAÓ��=ô),Ƭ1�ł+ŝûÂAÂĥ)vY�%ŝû°è�ij�=ƭIy_-gwƎ·ê+ŝûÂ�Ó��>$�=n|W|IJ) 2�ł+ŝûÂAÓ��=ô),Ƭ1�ł+ŝûÂAÂĥ)Iy_�&gw�%ŝû°è�ij�=ƭ
65
N�@OC
(a)&(b)+'!;+´ìy~_AƋ01��¡ā�:ƭÀ 2 A®Ş)�$:�ƭ
N61OC
(1) (a) (2) (b)
OH
COOH
COOH
OH
COOH
OH
(a)
(b) �
NO2 NO2H3C
NO2H3CH3C
(a)
(b)
(a)
(b)
ClCl
Cl
(1)
(2)
O
CH3
O
CH3
O
CH3
66
N�@OC
(1) ĕ+¨´Į+đƈßAŹ�ƭ(a)n|W|Ƭ(b)_yH|Ƭ(c)UZz|Ƭ(d)Dbx|Ƭ(e)b_{n|W|Ƭ(f)kGd~yƬ(g)DV_Dbx`Ƭ(h)RxZyƐƬ(i)ÎëƨƐƬ(j)M{{n|W|
(2) ĕ+¨´Į+đƈßAŹ�ƭ(a) o–MzX~yƬ(b) m–MzX~yƬ(c) p–MzX~y
(3) ĕ+°è):=ijìĮ+đƈAŋ�ƭ
(4) (a)&(b)��>+´ìy~_AƋ01��ƭÀ 2A®Ş)�$:�ƭ
N61OC
(1)(2) Ņķ (3)
(4) (b)
�
Br2Fe
Cl2hν
(a) (b)
CHO CHO
CH3
CHO
CH3CH3
(a)
(b)
Br
+HBr(a)
H Cl
Cl H
HClH Cl
ClHCl H
(b)