eh8@hg /1 )# part 2pub.maruzen.co.jp/book_magazine/yuki/web/workbook2/pdf/1.pdfhno3, h2so4 no2 br2,...
TRANSCRIPT
Part 2
1
(a) (b) (c)H3C CO
NH2
O N HOCH3
CH3
H3C C N(d)
δ–δ+(a) (b) (c) (d) C NB CN HH Br (e) Al H
δ+δ– δ–δ+ δ–δ+ δ–δ+
I–
Br CH
H
H+置換：(a)
CH3C H
CON
–
付加：(b)
+
O
CH C
H
H O H
–
H酸塩基反応：(c)
C CH
H H
HHO S+ CH3脱離：(d)
2
脱離
+(a)
(b)
(c)
(d)
H
NH H
H
OH H
+
O
CH3C Cl
+ CH3C Cl
OO–
O
CH3C OH
CCH2
H
Ph+ H Br
–
+
Cl
付加
酸塩基反応
付加
O H–
HN
H
H H
+
+
OH H
H
CH3C Cl
OO–
H
四面体中間体
+
CCH3
H
Ph–
Br+
–(b)
(c)
(d)
+H
OHH
+OHH+ O
H H
+H
OH H
(a)
O
COCH3CH2
H +
+ OS
O
O
OH
HO
NCH2CH2CH3
OH
NNH +H
OH H
+
–O
COCH3CH2
+ OH H
NNH H+
+ OH H
+ OS
O
O
OH
O
NCH2CH2CH3
H
+–
(e)
(e)O
COCH2CH3CH3
+H
OHH
+O
COCH2CH3CH3
H
+ OH H
+
(f) H2C CHC HH
H+ NH2
– H2C CHCH
H+ NH3
–
(e)
O
O
O
N
+H
OHH
+
O
O
+
OHH+
H
(d) OHS
O
O
HO+O
NO–S
O
O
HO+
+
H
(f) CH3 + NH2–
CH2– + NH3
–
(a)
(b)
(c)
F
BFF
OEt
Et+
O
MeMe+
Cl
AlClCl
OH
BOHHO
+ OH BOHHO
HO OH–
O
MeMe
AlCl
Cl Cl+
–
OEt
EtB
F
F
F
+–
SN1
3
+
OH
H
(a)
(b)
(c)
C BrH
Ph
Me
（求電子種） （求核種）
Ph
CHMe
+
（求電子種）
+
（求核種）
C OH
Ph
Me
H
H
+
（酸）
OH
H+
（塩基）
Ph
CHMe
+ Br–
C OH
Ph
Me
H
H
+
C OH
Ph
MeH
+ H OH
H+
(a)–O
HR HR
O C–
C N
N
+O
H H
HR
HO CNOH
–
求核付加 酸塩基反応
(b)O
HR+
(c)O
HR+ SPh
–
+
OH H
HR
O OH–
HR
HO OH
+HR
O SPh
HR
HO SPhH SPh
OH–
OH–
–
SPh–
HR
HO N
HR
O NH2–
R+
OH H
HR
HO NHRR
H
H+
OH– + H2O
HR
HO NHR +H
OHH HR
H2O NHR+
HR
NHR + OH2
HR
NR
+ H3O+
O
HR
+H
OHH
O
HR
H
+
OH H
+
HR
HO O
H
H+
HR
HO OHOH H +
H
OHH
O
OH
+
O
H
O
H
(a) +–
OHO
H
O
–
O
O–
+ H2O
H
O H–
OH
O
H
O
H
(b) + +H
OHH O
H
OH
H
+
+
O
OH
+O
OHH
O HH+H3O+
H2O
O
HR
+ O
HR
H
+
OH R'
+
HR
HO O
H
R'+
HR
R'O OR'
O R'H
H
HR
H2O OR'+ O
HR
R'
OH R'
+– H2O
HR
R'O O
H
R'+ R'OH
R'OH2+
(アセタール）
N
PhH
H
H Ph
OHN +
+PhH
NHO
+ +H
OHH
OH HH
H Ph
OH2NOH
+ O
PhH
+
HO
H
–– H+
（巻矢印省略）
+HO
H2N OH
O
OEtMe+
(四面体中間体）
O
OHMe+ EtO
–
+
– OH
OEtMe
O OH–
O
OMe– EtOH
酸塩基反応
H2O+
+O
OHMe
+O Et
H
H+
+
O Et
OHMe
HO O Et
H
+OH2Me
HO OEt
（四面体中間体）
O
OEtMe
H +
+O
OEtMe
O
OHMe
+ H
H
H3O+
O
OREt H O
H
H
++
O
OEtR
HO
H
H
+
OEtMe
HO O
H+ H
OEtMe
HO O+
H
H
O
OHR
H+
+ EtOHO
OHR+ EtOH
+ H+
BH4
– B B H C H
+O
Ph N
O
Ph N
H
O
ClPh+ HN
(四面体中間体）
ClPh
HO N
+ HCl+ Cl
ClPh
O N– H+
酸塩基反応
–
O
HPh+ B
H H
H H
HPh
O H+ B
H H
H
HOMe
HPh
HO H+ B
H H
H OMe
––
–
HPh
HO Me
MePh
HO Me
OHPh CO2HPh(a) (b) (c) (d)
O
OEt
OH(e)
O
HPh
+
+
O
HH
– OH
HH
O OH–
O
H OH
HPh
–O H
O
H O–
+
OHPh
酸塩基反応
4
BrPh(a)
OMe
BrPh
Me
BrPh
(b)Me
ClPh
Me
FPh
Me
IPh
(b)
SN2
E2 H Br
E2 H Br
NC OMe Cl OH
NCMe
H
MeCO
NH2Ph+
O
(a) (b)
(c) (d)
(b) (c)(a)
Br
H
MeH
Me
H
Br
H
H
–OEtMe
(主生成物）
+ EtOH+ Br–
(シス異性体）
H
H
MeBr
Me
Br
H
H
H
–OEtMe
(主生成物）
+ EtOH+ Br–
(トランス異性体）
HH H
HH H
Me
H H
Br
MePh
(2R,3R)
NaOMe
Me
Ph H
Me
Me
H Me
Br
HPh
(2S,3R)
NaOMe
Me
Ph Me
H
S
RR
R
5
H3O+
(a)OH
H OH
H+
OH2+
– H2O – H2O +Br
–
Br
(b)O H O
H
H+
O
– H2O
H
+
+HO+
I–
IHO+
OH+ H OSO3H
– HSO4– OH2
+– H2O
HH
+
O SO3H– HO SO3H+
OH
H OH
H+ – H2O
OH2+
– H2O
+
H
H
H H
+
Cl–
Cl
Ph NMe3 I–+
PhCH NHNH2CNH2
O
NMe2
O
Ph NMe2
(a) (b)
(c) (d)
6
SN2
H
OH H
+ Cl–
H
+
+H
OH
Cl–
HH
H
+
H
Cl
H2O
O
H OH
R+
O+
OH
R
HH
O O
O OR
OH
R
H OH
R+
+
R
H+
+ HBr
MeO
HBr Br Br
Br
+
OMe
Br
–Br
OMe
H
+
Br–
酸塩基反応
(a) (b)Br
Ph Br
Me
Br
Me
Br
Br
PhBr
H BrH
+
Br–
H+
Br–
H HBr
Br1,2–付加物 1,4–付加物
H
Br
3–ブロモ–1–ブテン
H+
Br–
HBr
1–ブロモ–2–ブテン
MeO CN
CN
(a) (b)O
O
O
(d)
OH
MeCO2Me
H
(c)Me
CO2Me+
CO2Me
Me（ラセミ体）
＋ エナンチオマー
（エキソ体は通常副生成物）
(a)O
+O
OH(b)
O
H
O
7
2 Br Al
Br Al
N OHO
OO S
O
O
OH– HSO4
– – H2OO N O
++
–
–
+
O
N
O
NH O
O
O SO3H
– H2SO4NO2
+
+–
+
硝酸 硫酸ニトロニウムイオン
ニトロベンゼン
付加 脱離
N OH2O
O+
–
H
Br Br AlBr3 Br Br AlBr3
+
–
Br Br AlBr3 BrH Br AlBr3
Br
+ –
+
+ HBr + AlBr3
ルイス酸塩基反応
付加
脱離
–
MeOアニソール
MeO
MeO
ClMe
OAlCl3
ClMe
O O
C
Me
AlCl4–
Me
O
AlCl3
O
Me
Cl AlCl3+
+–
+
–
AlCl3 O
Me
AlCl3
H2O
O
Me
+–
+ [Al(H2O)6]3+ + 3Cl–
Me Me
Me MeMe
トルエン
O
C
Me
AlCl4–+
アシリウムイオン
H – HCl
後処理
Me
MeC CH3
Me
MeHSO4
–+O S
O
O
OHH +
C MeMe
Me HCMe3
– H2SO4
+
O–
HO HO
+ SO3H
CMe3
HO
(a)F
PhH2C+
F
CH2Ph
(b)CCH3
CH3
O
Br
CCH3
O
CH3(c)
Br
(d)OMe
Cl NO2
(a) (b)
(c) (d)
CH2MeO CH2Cl
O CH2 NH C
O
O2N
NO2
O2N O2N
Cl
Cl2, AlCl3 HNO3, H2SO4(a)
NO2
Cl
OO
ClAlCl3
H2NNH2, KOH, 加熱または Zn(Hg), HCl, 加熱
または 1) HSCH2CH2SH, BF3·OEt2,
O
ClMe
(b)
2) Raney Ni
AlCl3Me
O
または H2, Pd
(c)NHAc
H2SO4NH2
NHAc
HO3S
NHAc
HO3S Br
Ac2O
AcONa
Br2, FeBr3NH2
Br
1) H3O+, 加熱
2) NaOH, H2O
8
(d)HNO3, H2SO4
NO2 Br2, FeBr3NO2Br
NH2BrまたはH2, Ni
1) Sn, HCl, 2) NaOH, H2O
O
HH
HH
OH–
+
O
HH
H
–
+ H2O
O
H3CH
HH
OH– O
H3CH
H
–Br Br O
H3CBr
HH
Br– H2O
O
EtOH
HH
O
EtOH
H
–
+ EtOHOEt
–
+O
HH
HH
+
HO
CH3H
OH
HH
H
H OH
H
+ HO
HH O
H
H
+
H OAc
OAc–
O OH+
HH
Br Br
Br–OH
H
AcOH
O+
BrH
HO
BrHBr
O
CH3H
O
HH
HH
OH– O
HH
H
–
H2O
O
H CH3
OH–
H OH O
H
OH
CH3OH
–+
O
Me Me
Me O+ OH
–H O
Me Me
Me O–
O
Me
O
MeMe–
+ H2O
HO
H
O
MeMe+ OH
–
E1cB
O
EtO
–
+ EtOH
OEt–
O
Me OEt
O
EtO OEt
O
Me
–
O
EtO Me
O O
EtO Me
O–
H H
O
PhHO
MeH
OH– O
Me
–
H2O
O
Me Ph
OH–
H OH O
Me
OH
Ph
OH–
+
H H
Me Ph
O OH–
H2O
O
Me PhOH
–
EtO
O
OEt
O
H
EtO
O
OEt
O
O
OEt
OEtO
– EtOH
O
OEt
O
H
O
OEt
OO
OEt
O
H OH2+
– H2O2) 酸処理
OEt–
OEt–
–
–
–
SN2
Me
O O
Me Me
O O
Me Me
O O
Me–
– –
OEt
O O
H HOEt
O O
OEt
O O–
– Cl–
Ph ClOEt– Ph
– EtOH
OO
O
OH
OO
OEt
OO
– CO2
HCl/H2O+
Br
加熱
NaOEt
EtOH
OEt
加水分解
脱炭酸
OEt
OO
EtO + Ph Br
HCl/H2O
OEt
OO
EtO
Ph
NaOEt
EtOH
Ph OH
O
OH
OO
HO
Ph
– CO2
加熱
HCN + HO– CN– + H2O
N N+
H3O+/H2O
NH2
+ +
SN2
加水分解Br
O
中間体O
Br– O
O+ Br–
N+
O
O H
HN O
H
H
O
+ N OH
O
+
H
OH+
NH
O+
O
NH2
+
O
+
O–
O+
–O
+
H C NO NC–
HO CN
O CN
–
NC–
+(a)
(c)
C O C C
BuLi
ON C–
–O
CN
H C N
CN
O
NC–
+
(b)
OEtO
OOEt
EtO H
OOEt
H
– EtO––
–
(a)
O+ H+
OH+EtOHOHOEt
H+ EtOH
OHOEt
+EtO–H
H
OOEt
H
H+ OOEt
– HCl
Cl
– EtOH
–
(b)
(a) (b)O
OEt
CNO
H
O(c)
OH
(d) (e)Et2NCN
O
EtO2C
CO2Et
O
H OO
O
OO
OH OEt
O
O
HOO
H OEt
HH
Michael
OEt–
–
反応
アルドール
–
–
–
OEt–
E1cB 脱離
H
H
O
O
OH
OOH
OEt–
–
反応
NO
+
N O
H OEt
+
– EtO–
N O+
–
H3O+, H2O
OO
H2N+加水分解 +
Cl OMe
NO O
Cl OMe
NO O
Cl OMe
NO
Cl OMe
NO O
–
+ –––– O+ + +
–
–
–
Cl
–
– NH3 – Cl–Cl
H
NH2
–
NH2
–
NH2
NH2
––NH2
––NH2
H NH2
H NH2ベンザイン中間体
NH2–
NH2–
Me
Me
Me
Me
Me Me
Me
+OHH+
OH2– H2O
+
+
H– H+
1,2–
Br
H
HH
H
– Br– +H
H
+
HO
H
H
O
H
H
H+
HO
H H
H
OH
– H3O+
OTs H
H
+
– H+– TsO–
H
H
OH+
– H2O
HOH
OHH
(a) H+H
OH2
OHH
+
H
OHH
+
– H+H
H
O
– TsO–
OH+
HOH
OTsH
HOH
OHH
TsCl
H H
O
– H+
(b) OTs
OH
HH
回転
O–
OHH+ OH+
H
OH+
O– H+
O
OH
+ H+OH
OH
+OH
OH
OH
O
– H+
+
1,2–移動
O
OH
HO–O
O
O
O
OH
O
H–OH– HO–
–
–
O
PhPh
OOH
–
PhPh
PhOH
O
O
–
–
O OH–
OPh
O
OPh
OHPh
1,2–移動O–OHPh
Me Me + H+
O–OH2Ph
Me Me+
OPh
Me Me+
OH2
Me Me+OH2PhO
Me Me+
OHPhOH
Me MePhOH +
OH+
– H+ O
MeMe
PhOH +
N
MePh
OH+ H+ N
MePh
OH2+
N
Me
Ph
+
N
Me
Ph+
OH2
N
OH2Me
Ph
+
N
OHMe
Ph + HN
OHMe
Ph
+
H– H+ N
OMe
Ph H
1,2–移動
Ph
Me MeCl
H Ht-BuO
CHPh
Me Me
– カルベン
Me
MeH
Ph– Cl–
1,2–移動O
NR
O
R NH
H
NaOH, Br2
OH
O
R NH
Br–BrO
R NBr
H– H2O – Br–
N C OR– CO2
+ HO–
NH–CO2–R RNH2
O
R NBr
– H2O
+ H+
アシルニトレン イソシアナート
–
–
OH–
–
– Br–
N N CMe2Me2C
CNCNMe2C
CN
2 + N N
+ Br
RO OR 2 RO
RO H Br RO H
C CH2
CH3
HBr C C
CH3
H
BrH2
C CH2BrCH3
HH Br C CH2BrCH3
H
H
+ Br
加熱開始段階：
成長段階：
CH3
Br
H Br+
Br Br+ Br
H H H
CH3
H
CH3 CH3
H Br
Cl RBu3Sn Bu3Sn–Cl + R
R H SnBu3 R–H SnBu3+
1,2–
Me O6 O–
2
MeO
Me MeOTs
H2O+OMe
Me
Me
Me
MeOMe+
H H
Me
Me HOMe+
Me
Me H
OH2
OMe
+
Me
Me H
OH
OMe+H
HHMe
Me H
OH
H
+MeOH
Me
Me
O
H– H+
TsO–
H+
O
Me
+HO
Me
HO
Me+
Me
HO
Me
OH
++
H
Me
OH
– H+
O O
O
O O O
2–1
移動
O
PhH H Oi-Pr
–
O
Ph
–
– i-PrOH O
H
O
Ph
O–
O
H
O
Ph
O
–
i-PrH
O
OHPh
O O
i-Pr–
Li+
ヒドリド O
Ph
O
O
i-Pr–
Li+MeOH
OH
Ph
O
O
i-Pr
OH–
加水分解
OH
Ph
O i-Pr
O OH–
OH
Ph
O–
O
OHi-Pr+
OH
Ph
OH
–
O
Oi-Pr+
反応アルドール
O
PhPh
H H OH–
O
PhPh
–
HO
PhPh
O
O
Ph
O
Ph
PhH
PhO
–
H2O
O
Ph
O
Ph PhOH
O
Ph
O
Ph
PhH
PhOH
OH– Ph
–
E1cB
アルドール
Ph
O
Ph
Ph
O
Ph– H2O
同じようにPh
O
Ph
Ph
O–
Ph
HO–
O
PhPh
PhOHPhH2O
アルドール
HE1cB
– H2O
O
PhPh
Ph Ph
O
MeO
OMe–
–
O
MeO OMe
Me
O
OMe
O
–
O
Me
OOMe
–
Me
O O OMe–
Me
O OH
OMe–
O
Me
O–
– MeOH